Synthetic compounds useful as nodulation agents of leguminous plants and preparation processes thereof

ABSTRACT

The present invention relates to synthetic compounds that are active on plants, especially as legume nodulation factors, and also as plant growth stimulators, and to methods for preparing such compounds, which are of formula (I):

CROSS-REFERENCE TO RELATED APPLICATION(S)

The present application is a 35 U.S.C. §371 national phase conversion ofPCT/EP2004/014909 filed Dec. 22, 2004, which claims priority of FrenchApplication No. 0315543 filed Dec. 30, 2003.

BACKGROUND OF THE INVENTION

The present invention relates to synthetic compounds that are active onplants, especially as legume nodulation factors, and also as plantgrowth stimulators, and to methods for preparing such compounds.

It is known that the process of nitrogen fixing by legumes is based onsymbiosis between these plants and soil bacteria, the Rhizobia. TheRhizobium-legume symbiosis produces each year, by means of the rootnodules, more ammonium than all of the nitrogen fertilizer industry.This symbiosis thus plays a considerable agronomic role. Legumes arevery rich in proteins and produce about one third of the plant proteinsconsumed worldwide, by virtue of pulses such as soybean, pea, horsebean, groundnut, bean and lupin, and forage plants such as alfalfa andclover.

The formation of nitrogen-fixing nodules starts with an exchange ofmolecular signals, flavonoids secreted by the plant and nodulationfactors (Nod factors) synthesized by the bacterium. These factorsconsist of an oligosaccharide fragment and a lipid chain attached tothis skeleton on the non-reducing end. They have structural attributes(substitutions on the sugars at the two ends and variability of thechain) that make them specific to the legume-bacterium couple.

These lipochito-oligosaccharides (LCO) may be either isolated directlyfrom a particular culture of rhizobia, synthesized chemically, orobtained chemo-enzymatically. Via the latter method, the oligosaccharideskeleton may be formed by culturing of recombinant Escherichia colibacterial strains in a fermenter, and the lipid chain may then beattached chemically.

Treatment of the seeds of legumes, for instance soybean, with Nodfactors at very low concentrations, may result in a large increase inthe number of nitrogen-fixing root nodules and a significant increase inthe yields, under agronomic conditions. It is thus clear that, in thefuture, compounds of Nod factor type will be produced industrially forlarge-scale agronomic use. However, the industrial preparation andconditioning of natural Nod factors presents two types of drawback: (1)the natural Nod factors are difficult to assay via simple methods suchas spectrometric methods; (2) they are unstable in the presence ofplants or in soils, in particular because they have a —CO—NH— bond thatmay be broken by plant or microbial enzymes present in the rhizosphere.

BRIEF SUMMARY OF THE INVENTION

One of the aspects of the present invention is to propose a process forpreparing compounds of Nod factor type, some of these compoundsconstituting another aspect of the invention. Specifically, certainbiologically active compounds show strong absorption in the ultravioletrange, which makes them easy to assay during their industrialpreparation and allows them to be detected and assayed easily in theproduct intended for marketing, and allows their stability and storagein such products to be tested. In addition, some of these synthesizedcompounds show higher stability than the natural Nod factors.

The compounds described may be used to treat plants or plant parts. Theterm “plants” means wild plants and also crop plants (including futurecrop plants). The crop plants may be derived either from conventionalvariety-selection methods, from genetic engineering methods, or from acombination of these two methods. The term “plant parts” means all theaerial or subterranean plant parts or organs, such as flowering-plantseed, root, tuber, rhizome, germ, stalk, leaf and flower. Also includedin the category of plant parts are the harvest products and also thereproductive vegetative or germinative material, such as rhizome, tuber,seed, bud or graft.

The compounds described may be used to treat plants or plant partsdirectly or via the action of their environment or of their culture orstorage medium. The usual treatment methods are, for example, dipping,vaporization, evaporation, spraying, spread and application, and for thereproductive material, in particular for the seeds, simple or multilayercoating.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the activity of the benzamide derivative 3meta-substituted with the undec-4Z -enyloxy chain.

FIG. 2 illustrates the relative activities of the benzyl derivative 4 tothe benzamide derivative 3.

FIG. 3 illustrates the relative response and activity of theN-acetylation of the benzyl derivative 4 with the benzamide derivative3.

FIG. 4 illustrates the activity with an unsaturation in position 4.

FIG. 5 illustrates test sensitivity.

DETAILED DESCRIPTION OF THE INVENTION

In the case of treating the reproductive material, especially seeds, thecompounds described may be applied alone or in combination with otheractive molecules such as fungicides, insecticides, acaricides,nematicides, growth regulators and herbicides. The compounds describedand their combinations with active molecules belonging to the abovementioned families may be applied directly or using a suitableformulation. This formulation may be diluted or film-forming agents maybe added thereto before use. The use may take place at any of the stepsof handling of the seeds between harvesting and sowing, including duringself-seeding. Suitable formulations and processes for treating seeds areknown to those skilled in the art and are described, inter alia, in thefollowing documents: U.S. Pat. Nos. 4,272,417 A, 4,245,432 A, 4,808,430A, 5,876,739 A, US 2003/0176428 A1, WO 2002/080675 A1, WO 2002/028186A2.

The formulations usually used may be solutions, emulsions, suspensions,powders, spraying powders, pastes, soluble pastes, gels, granules,concentrated suspo-emulsions, natural or synthetic impregnatedmaterials, and also microencapsulation using polymers. Theseformulations are commonly prepared, for example, by mixing the compoundsdescribed and/or combinations thereof with other active molecules withsolid or liquid formulation supports, using, where appropriate,emulsifying and/or dispersing and/or foaming surfactants. They may alsocontain a dye such as mineral pigments.

The target Nod factor is especially the factor associated with alfalfa(1) as described above. Among all the existing legumes, alfalfa andvetch have been the subject of numerous studies. By virtue of severalactivity tests performed with various Nod factor analogs, it has beenpossible to establish a relationship between the structure of the LCOand the plant response. The isolated nodulation factor that is mostactive on alfalfa is a tetramer sulfated in position 6 of the reducingsugar, acetylated in position 6 of the sugar located at the nonreducingend and acylated with a chain of 16 carbons containing two unsaturations(C16:2Δ2E,9Z) (1)

It has been shown that the absence of acetate, the addition of aglucosamine unit, or the loss of one of the two unsaturations produceonly a moderate reduction in activity. A test of variation of the chainlength revealed maximum activity for a chain of 16 carbons. Finally, thesulfate is of prime importance for recognition of the Nod factor byalfalfa, but, on the other hand, its absence is necessary for action invetch.

Studies have shown that the conjugated unsaturation present at 2 of thelipid chain was important for nodulation, since an analog acylated witha C16:1Δ9Z chain is less active (by just under a factor of 10).

From these results, a series of analogs for which the conjugated amidebond is mimicked by a benzamide bond have been prepared. These compoundsconstitute one of the aspects of the present invention. Another seriesof analogs containing a function of benzylamine type constitute anotheraspect of the invention.

Such compounds are capable of causing or promoting the phenomenon ofnodulation in legumes and of stimulating plant growth and development.

The compounds that are plant nodulation factors according to theinvention are preferably compounds of formula (I)

in which

-   -   n represents 1, 2 or 3;    -   A represents a substituent chosen from —C(O)—, —C(S)—, —CH₂—,        —CHR¹⁰—, —CR¹⁰R¹¹—, —C(O)O—, —C(O)S—, —C(S)O—, —C(S)S—,        —C(O)NH—, —C(NH)NH— and —C(S)NH—;    -   B represents        -   an arylene;        -   a heteroarylene comprising 1 or 2 hetero atoms chosen from            nitrogen, oxygen and sulfur;        -   a naphthylene;        -   a heteronaphthylene comprising 1 or 2 hetero atoms chosen            from nitrogen, oxygen and sulfur;        -   a divalent radical derived from 2 fused aromatic rings of 5            or 6 atoms each;        -   a divalent radical derived from 2 fused aromatic or            heteroaromatic rings of 5 or 6 atoms each, comprising 1 or 2            hetero atoms chosen from nitrogen, oxygen and sulfur;        -   a biphenylene;        -   or a heterobiphenylene comprising 1 or 2 hetero atoms chosen            from nitrogen, oxygen and sulfur;            these groups possibly being substituted with one or two            substituents R¹² and R¹³ chosen, independently of each            other, from halogen, CN, C(O)OR¹⁴, C(O)NR¹⁵R¹⁶, CF₃, OCF₃,            —NO₂, N₃, OR¹⁴, SR¹⁴, NR¹⁵R¹⁶ and C₁₋₆-alkyl;    -   C represents a substituent chosen from —O—, —S—, —CH₂—, —CHR¹⁷—,        —CR¹⁷R¹⁸— and —NR¹⁹;    -   D represents a linear or branched, saturated or unsaturated        hydrocarbon-based chain containing from 2 to 20 carbon atoms;    -   E and G represent, independently of each other, a substituent        chosen from H, OH, OR²⁰, NH₂ and NHR²⁰;    -   R¹ represents a substituent chosen from H, C₁₋₆-alkyl, C(O)H and        C(O)CH₃;    -   R², R³, R⁶, R¹⁴, R¹⁵, R¹⁶ and R¹⁹ represent, independently of        each other, a substituent chosen from H, C₁₋₆-alkyl,        C(O)C₁₋₆-alkyl, —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂,        —C(S)NH₂, —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and        —C(NH)NHC₁₋₆-alkyl;    -   R⁴ represents a substituent chosen from H, C₁₋₆-alkyl and R²¹;    -   R⁵ represents a substituent chosen from H, C₁₋₆-alkyl, fucosyl        and R²²;    -   R⁷ represents a substituent chosen from H, C₁₋₆-alkyl,        arabinosyl and R²³;    -   R⁸ represents a substituent chosen from H, C₁₋₆-alkyl, fucosyl,        methylfucosyl, sulfofucosyl, acetylfucosyl, arabinosyl, SO₃H,        SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄ and R²⁴;    -   R⁹ represents a substituent chosen from H, C₁₋₆-alkyl, mannose,        glycerol and R²⁵;    -   R¹⁰, R¹¹, R¹⁷ and R¹⁸ represent, independently of each other, a        substituent chosen from C₁₋₆-alkyl and F;    -   R²⁰, R²¹, R²², R²³, R²⁴ and R²⁵ represent, independently of each        other, a substituent chosen from C(O)C₁₋₆-alkyl,        —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,        —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and        —C(NH)NHC₁₋₆-alkyl;        and also the possible geometrical and/or optical isomers,        enantiomers and/or diastereoisomers, tautomers, salts, N-oxides,        sulfoxides, sulfones, metal or metalloid complexes thereof,        which are agriculturally acceptable. Among the compounds defined        above, the most important compounds are the salts, more        particularly the lithium, sodium, potassium or        tetraalkylammonium salts.

Preferably, the compounds of formula (I) have one or other of thefollowing characteristics, taken separately or in combination:

-   -   n represents 2 or 3;    -   A represents —C(O)— or —CH₂—;    -   B represents a phenylene;    -   C represents —O—;    -   D represents a linear, saturated or unsaturated        hydrocarbon-based chain containing from 3 to 17 carbon atoms;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H, CH₃ or C(O)CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl.

Among these compounds, the ones that are preferred are those of formula(I) simultaneously having the following characteristics:

-   -   n represents 2 or 3;    -   A represents —C(O)— or —CH₂—;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H, CH₃ or C(O)CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl;        even more preferably, those simultaneously having the following        characteristics:    -   n represents 2 or 3;    -   A represents —C(O)— or —CH₂—;    -   D represents a linear, saturated or unsaturated        hydrocarbon-based chain containing from 3 to 17 carbon atoms;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H, CH₃ or C(O)CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl;        and most preferably the compounds of formula (I) simultaneously        having the following characteristics:    -   n represents 2 or 3;    -   A represents —C(O)— or —CH₂—;    -   C represents —O—;    -   D represents a linear, saturated or unsaturated        hydrocarbon-based chain containing from 3 to 17 carbon atoms;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H, CH₃ or C(O)CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl.

Among these preferred compounds, mention may be made of the compounds offormula (I) simultaneously having the following characteristics:

-   -   n represents 2 or 3;    -   A represents —C(O)— or —CH₂—;    -   B represents a phenylene;    -   C represents —O—;    -   D represents a linear hydrocarbon-based chain containing 11        carbons, which is saturated, or unsaturated between carbons 4        and 5;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H, CH₃ or C(O)CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl.

Among the compounds of the present invention, the compounds for which Arepresents a carbonyl group are particularly advantageous, and may berepresented by formula (Ia):

in which

-   -   n represents 1, 2 or 3,    -   B represents        -   an arylene;        -   a heteroarylene comprising 1 or 2 hetero atoms chosen from            nitrogen, oxygen and sulfur;        -   a naphthylene;        -   a heteronaphthylene comprising 1 or 2 hetero atoms chosen            from nitrogen, oxygen and sulfur;        -   a divalent radical derived from 2 fused aromatic rings            containing 5 or 6 atoms each;        -   a divalent radical derived from 2 fused heteroaromatic rings            containing 5 or 6 atoms each, and comprising 1 or 2 hetero            atoms chosen from nitrogen, oxygen and sulfur;        -   a biphenylene;        -   or a heterobiphenylene comprising 1 or 2 hetero atoms chosen            from nitrogen, oxygen and sulfur;            these groups possibly being substituted with one or two            substituents R¹² and R¹³ chosen, independently of each            other, from halogen, CN, C(O)OR¹⁴, C(O)NR¹⁵R¹⁶, CF₃, OCF₃,            —NO₂, N₃, OR¹⁴, SR¹⁴, NR¹⁵R¹⁶ and C₁₋₆-alkyl;    -   C represents a substituent chosen from —O—, —S—, —CH₂—, —CHR¹⁷—,        —CR¹⁷R¹⁸—, —NH— and —NR¹⁹;    -   D represents a linear or branched, saturated or unsaturated        hydrocarbon-based chain containing from 2 to 20 carbon atoms;    -   E and G represent, independently of each other, a substituent        chosen from H, OH, OR²⁰, NH₂ and NHR²⁰;    -   R¹ represents a substituent chosen from H, C₁₋₆-alkyl, C(O)H and        C(O)CH₃;    -   R², R³ and R⁶ represent, independently of each other, a        substituent chosen from H, C₁₋₆-alkyl, C(O)C₁₋₆-alkyl,        —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,        —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and        —C(NH)NHC₁₋₆-alkyl;    -   R⁴ represents a substituent chosen from H, C₁₋₆-alkyl and R²¹;    -   R⁵ represents a substituent chosen from H, C₁₋₆-alkyl, fucosyl        and R²²;    -   R⁷ represents a substituent chosen from H, C₁₋₆-alkyl,        arabinosyl and R²³;    -   R⁸ represents a substituent chosen from H, C₁₋₆-alkyl, fucosyl,        methylfucosyl, sulfofucosyl, acetylfucosyl, arabinosyl, SO₃H,        SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄ and R²⁴;    -   R⁹ represents a substituent chosen from H, C₁₋₆-alkyl, mannose,        glycerol and R²⁵;    -   R¹⁰, R¹¹, R¹⁷ and R¹⁸ represent, independently of each other, a        substituent chosen from C₁₋₆-alkyl and F;    -   R¹⁴, R¹⁵, R¹⁶ and R¹⁹ represent, independently of each other, a        substituent chosen from H, C₁₋₆-alkyl, —C(O)C₁₋₆-alkyl,        —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,        —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and        —C(NH)NHC₁₋₆-alkyl;    -   R²⁰, R²¹, R²², R²³, R²⁴ and R²⁵ represent, independently of each        other, a substituent chosen from C(O)C₁₋₆-alkyl,        —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,        —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and        —C(NH)NHC₁₋₆-alkyl;        and also the possible geometrical and/or optical isomers,        enantiomers and/or diastereoisomers, tautomers, salts, N-oxides,        sulfoxides, sulfones, metal or metalloid complexes thereof,        which are agriculturally acceptable. Among the compounds defined        above, the most important compounds are the salts, more        particularly the lithium, sodium, potassium, or        tetraalkyl-ammonium salts.

Among these compounds of formula (Ia) the ones that are preferred arethose having the following characteristics, taken separately or incombination:

-   -   n represents 2 or 3;    -   B represents a phenylene;    -   C represents —O—;    -   D represents a linear, saturated or unsaturated        hydrocarbon-based chain containing from 3 to 17 carbon atoms;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl;        more preferably, those simultaneously having the following        characteristics:    -   n represents 2 or 3;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl;        even more preferably, those simultaneously having the following        characteristics:    -   n represents 2 or 3;    -   D represents a linear, saturated or unsaturated        hydrocarbon-based chain containing from 3 to 17 carbon atoms;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl.

Among these compounds of formula (Ia), the ones that are more preferredare those simultaneously having the following characteristics:

-   -   n represents 2 or 3;    -   C represents —O—;    -   D represents a linear, saturated or unsaturated        hydrocarbon-based chain containing from 3 to 17 carbon atoms;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl;        or those simultaneously having the following characteristics:    -   n represents 2 or 3;    -   B represents a phenylene;    -   C represents —O—;    -   D represents a linear hydrocarbon-based chain containing 11        carbons, which is saturated, or unsaturated between carbons 4        and 5;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl.

Among the compounds of the present invention, the compounds for which Arepresents a methylene group are also particularly advantageous, and maybe represented by formula (Ib):

in which

-   -   n represents 1, 2 or 3;    -   B represents        -   an arylene;        -   a heteroarylene comprising 1 or 2 hetero atoms chosen from            nitrogen, oxygen and sulfur;        -   a naphthylene;        -   a heteronaphthylene comprising 1 or 2 hetero atoms chosen            from nitrogen, oxygen and sulfur;        -   a divalent radical derived from 2 fused aromatic rings each            containing 5 or 6 atoms;        -   a divalent radical derived from 2 fused aromatic or            heteroaromatic rings each containing 5 or 6 atoms,            comprising 1 or 2 hetero atoms chosen from nitrogen, oxygen            and sulfur;        -   a biphenylene;        -   or a heterobiphenylene comprising 1 or 2 hetero atoms chosen            from nitrogen, oxygen and sulfur;            these groups possibly being substituted with one or two            substituents R¹² and R¹³ chosen, independently of each            other, from halogen, CN, C(O)OR¹⁴, C(O)NR¹⁵R¹⁶, CF₃, OCF₃,            —NO₂, N₃, OR¹⁴, SR¹⁴, NR¹⁵R¹⁶ and C₁₋₆-alkyl;    -   C represents a substituent chosen from —O—, —S—, —CH₂—, —CHR¹⁷—,        —CR¹⁷R¹⁸—, —NH— and —NR¹⁹;    -   D represents a linear or branched, saturated or unsaturated        hydrocarbon-based chain containing from 2 to 20 carbon atoms;    -   E and G represent, independently of each other, a substituent        chosen from H, OH, OR²⁰, NH₂ and NHR²⁰;    -   R¹ represents a substituent chosen from H, C₁₋₆-alkyl, C(O)H and        C(O)CH₃;    -   R², R³ and R⁶ represent, independently of each other, a        substituent chosen from H, C₁₋₆-alkyl, C(O)C₁₋₆-alkyl,        —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,        —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and        —C(NH)NHC₁₋₆-alkyl;    -   R⁴ represents a substituent chosen from H, C₁₋₆-alkyl and R²¹;    -   R⁵ represents a substituent chosen from H, C₁₋₆-alkyl, fucosyl        and R²²;    -   R⁷ represents a substituent chosen from H, C₁₋₆-alkyl,        arabinosyl and R²³;    -   R⁸ represents a substituent chosen from H, C₁₋₆-alkyl, fucosyl,        methylfucosyl, sulfo-fucosyl, acetylfucosyl, arabinosyl, SO₃H,        SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄ and R²⁴;    -   R⁹ represents a substituent chosen from H, C₁₋₆-alkyl, mannose,        glycerol and R²⁵;    -   R¹⁰, R¹¹, R¹⁷ and R¹⁸ represent, independently of each other, a        substituent chosen from C₁₋₆-alkyl and F;    -   R¹⁴, R¹⁵, R¹⁶ and R¹⁹ represent, independently of each other, a        substituent chosen from H, C₁₋₆-alkyl, —C(O)C₁₋₆-alkyl,        —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,        —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and        —C(NH)NHC₁₋₆-alkyl;    -   R²⁰, R²¹, R²², R²³, R²⁴ and R²⁵ represent, independently of each        other, a substituent chosen from C(O)C₁₋₆-alkyl,        —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,        —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and        —C(NH)NHC₁₋₆-alkyl;        and also the possible geometrical and/or optical isomers,        enantiomers and/or diastereoisomers, tautomers, salts, N-oxides,        sulfoxides, sulfones, metal or metalloid complexes thereof,        which are agriculturally acceptable. Among the compounds defined        above, the most important compounds are the salts, more        particularly the lithium, sodium, potassium or        tetraalkyl-ammonium salts.

Among these compounds of formula (Ib) the ones that are preferred arethose having the following characteristics, taken separately or incombination:

-   -   n represents 2 or 3;    -   B represents a phenylene;    -   C represents —O—;    -   D represents a linear, saturated or unsaturated        hydrocarbon-based chain containing from 3 to 17 carbon atoms;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or C(O)CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl;        more preferably, those simultaneously having the following        characteristics:    -   n represents 2 or 3;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or C(O)CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl;        even more preferably, those simultaneously having the following        characteristics:    -   n represents 2 or 3;    -   D represents a linear, saturated or unsaturated        hydrocarbon-based chain containing from 3 to 17 carbon atoms;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or C(O)CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl.

Among these compounds of formula (Ib), the ones that are more preferredare those simultaneously having the following characteristics:

-   -   n represents 2 or 3;    -   C represents —O—;    -   D represents a linear, saturated or unsaturated        hydrocarbon-based chain containing from 3 to 17 carbon atoms;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or C(O)CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂,    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl;        or those simultaneously having the following characteristics:    -   n represents 2 or 3;    -   B represents a phenylene;    -   C represents —O—;    -   D represents a linear hydrocarbon-based chain containing 11        carbons, which is saturated, or unsaturated between carbons 4        and 5;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or C(O)CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl.

Among the compounds of the present invention, the compounds for which Crepresents an oxygen atom are also particularly advantageous, and may berepresented by formula (Ic):

in which

-   -   n represents 1, 2 or 3, preferably 2 or 3;    -   A represents a substituent chosen from —C(O)—, —C(S)—, —CH₂—,        —CHR¹⁰—, —CR¹⁰R¹¹—, —C(O)O—, —C(O)S—, —C(S)O—, —C(S)S—,        —C(O)NH—, —C(NH)NH— and —C(S)NH—, preferably —C(O)—;    -   B represents        -   an arylene;        -   a heteroarylene comprising 1 or 2 hetero atoms chosen from            nitrogen, oxygen and sulfur;        -   a naphthylene;        -   a heteronaphthylene comprising 1 or 2 hetero atoms chosen            from nitrogen, oxygen and sulfur;        -   a divalent radical derived from 2 fused aromatic rings            containing 5 or 6 atoms each;        -   a divalent radical derived from 2 fused aromatic or            heteroaromatic rings containing 5 or 6 atoms each,            comprising 1 or 2 hetero atoms chosen from nitrogen, oxygen            and sulfur;        -   a biphenylene;        -   or a heterobiphenylene comprising 1 or 2 hetero atoms chosen            from nitrogen, oxygen and sulfur;            these groups possibly being substituted with one or two            substituents R¹² and R¹³ chosen, independently of each            other, from halogen, CN, C(O)OR¹⁴, C(O)NR¹⁵R¹⁶, CF₃, OCF₃,            —NO₂, N₃, OR¹⁴, SR¹⁴, NR¹⁵R¹⁶ and C₁₋₆-alkyl;    -   D represents a linear or branched, saturated or unsaturated        hydrocarbon-based chain containing from 2 to 20 carbon atoms,        preferably a linear hydrocarbon-based chain containing 11        carbons, which is saturated, or unsaturated between carbons 4        and 5;    -   E and G represent, independently of each other, a substituent        chosen from H, OH, OR²⁰, NH₂ and NHR²⁰, preferably NHC(O)CH₃;    -   R¹ represents a substituent chosen from H, C₁₋₆-alkyl, C(O)H and        C(O)CH₃, preferably H or CH₃;    -   R², R³ and R⁶ represent, independently of each other, a        substituent chosen from H, C₁₋₆-alkyl, —C(O)C₁₋₆-alkyl,        —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,        —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and        —C(NH)NHC₁₋₆-alkyl; preferably H;    -   R⁴ represents a substituent chosen from H, C₁₋₆-alkyl and R²¹,        preferably H, C(O)CH₃ or C(O)NH₂;    -   R⁵ represents a substituent chosen from H, C₁₋₆-alkyl, fucosyl        and R²², preferably H;    -   R⁷ represents a substituent chosen from H, C₁₋₆-alkyl,        arabinosyl and R²³, preferably H;    -   R⁸ represents a substituent chosen from H, C₁₋₆-alkyl, fucosyl,        methylfucosyl, sulfofucosyl, acetylfucosyl, arabinosyl, SO₃H,        SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄ and R²⁴, preferably H,        SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄, fucosyl or        methylfucosyl;    -   R⁹ represents a substituent chosen from H, C₁₋₆-alkyl, mannose,        glycerol and R²⁵, preferably H;    -   R¹⁰, R¹¹, R¹⁷ and R¹⁸ represent, independently of each other, a        substituent chosen from C₁₋₆-alkyl and F;    -   R¹⁴, R¹⁵, R¹⁶ and R¹⁹ represent, independently of each other, a        substituent chosen from H, C₁₋₆-alkyl, —C(O)C₁₋₆-alkyl,        —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,        —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and        —C(NH)NHC₁₋₆-alkyl;    -   R²⁰, R²¹, R²², R²³, R²⁴ and R²⁵ represent, independently of each        other, a substituent chosen from C(O)C₁₋₆-alkyl,        —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,        —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and        —C(NH)NHC₁₋₆-alkyl;        and also the possible geometrical and/or optical isomers,        enantiomers and/or diastereoisomers, tautomers, salts, N-oxides,        sulfoxides, sulfones, metal or metalloid complexes thereof,        which are agriculturally acceptable. Among the compounds defined        above, the most important compounds are the salts, more        particularly the lithium, sodium, potassium or        tetraalkylammonium salts.

Among the compounds of formula (Ic), the ones that are preferred arethose having one or other of the following characteristics, takenseparately or in combination:

-   -   n represents 2 or 3;    -   A represents —C(O)— or —CH₂—;    -   B represents a phenylene;    -   D represents a linear, saturated or unsaturated        hydrocarbon-based chain containing from 3 to 17 carbon atoms;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H, CH₃ or C(O)CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl;        more preferably, those simultaneously having the following        characteristics:    -   n represents 2 or 3;    -   A represents —C(O)— or —CH₂—;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H, CH₃ or C(O)CH₃;    -   R², R³, R⁵, R⁶,R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl;        even more preferably, those simultaneously having the following        characteristics:    -   n represents 2 or 3;    -   A represents —C(O)— or —CH₂—;    -   D represents a linear, saturated or unsaturated        hydrocarbon-based chain containing from 3 to 17 carbon atoms;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H, CH₃ or C(O)CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl;        most preferably, those simultaneously having the following        characteristics:    -   n represents 2 or 3;    -   A represents —C(O)— or —CH₂—;    -   B represents a phenylene;    -   D represents a linear hydrocarbon-based chain containing 11        carbon atoms, which is saturated, or unsaturated between carbons        4 and 5;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H, CH₃ or C(O)CH₃;    -   R², R³, ⁵ R⁵, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl.

Among the compounds of the present invention, the compounds for which Arepresents a carbonyl group and C represents an oxygen atom are mostparticularly advantageous, and may be represented by formula (Id):

in which

-   -   n represents 1, 2 or 3, preferably 2 or 3;    -   B represents        -   an arylene;        -   a heteroarylene comprising 1 or 2 hetero atoms chosen from            nitrogen, oxygen and sulfur;        -   a naphthylene;        -   a heteronaphthylene comprising 1 or 2 hetero atoms chosen            from nitrogen, oxygen and sulfur;        -   a divalent radical derived from 2 fused aromatic rings each            containing 5 or 6 atoms;        -   a divalent radical derived from 2 fused aromatic or            heteroaromatic rings each containing 5 or 6 atoms,            comprising 1 or 2 hetero atoms chosen from nitrogen, oxygen            and sulfur;        -   a biphenylene;        -   or a heterobiphenylene comprising 1 or 2 hetero atoms chosen            from nitrogen, oxygen and sulfur;            these groups possibly being substituted with one or two            substituents R¹² and R¹³ chosen, independently of each            other, from halogen, CN, C(O)OR¹⁴, C(O)NR¹⁵R¹⁶, CF₃, OCF₃,            —NO₂, N₃, OR¹⁴, SR¹⁴, NR¹⁵R¹⁶ and C₁₋₆-alkyl;    -   D represents a linear or branched, saturated or unsaturated        hydrocarbon-based chain containing from 2 to 20 carbon atoms,        preferably a linear hydrocarbon-based chain containing 11 carbon        atoms, which is saturated, or unsaturated between carbons 4 and        5;    -   E and G represent, independently of each other, a substituent        chosen from H, OH, OR²⁰, NH₂ and NHR²⁰, preferably NHC(O)CH₃;    -   R¹ represents a substituent chosen from H, C₁₋₆-alkyl, C(O)H and        C(O)CH₃, preferably H or CH₃;    -   R², R³ and R⁶ represent, independently of each other, a        substituent chosen from H, C₁₋₆-alkyl, —C(O)C₁₋₆-alkyl,        —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,        —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and        —C(NH)NHC₁₋₆-alkyl; preferably H;    -   R⁴ represents a substituent chosen from H, C₁₋₆-alkyl and R²,        preferably H, C(O)CH₃ or C(O)NH₂;    -   R⁵ represents a substituent chosen from H, C₁₋₆-alkyl, fucosyl        and R²², preferably H;    -   R⁷ represents a substituent chosen from H, C₁₋₆-alkyl,        arabinosyl and R²³, preferably H;    -   R⁸ represents a substituent chosen from H, C₁₋₆-alkyl, fucosyl,        methylfucosyl, sulfofucosyl, acetylfucosyl, arabinosyl, SO₃H,        SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄ and R²⁴, preferably H,        SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄, fucosyl or        methylfucosyl;    -   R⁹ represents a substituent chosen from H, C₁₋₆-alkyl, mannose,        glycerol and R²⁵, preferably H;    -   R¹⁰, R¹¹, R¹⁷ and R¹⁸ represent, independently of each other, a        substituent chosen from C₁₋₆-alkyl and F;    -   R¹⁴, R¹⁵, R¹⁶ and R¹⁹ represent, independently of each other, a        substituent chosen from H, C₁₋₆-alkyl, —C(O)C₁₋₆-alkyl,        —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,        —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and        —C(NH)NHC₁₋₆-alkyl;    -   R²⁰, R²¹, R²², R²³, R²⁴ and R²⁵ represent, independently of each        other, a substituent chosen from —C(O)C₁₋₆-alkyl,        —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,        —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and        —C(NH)NHC₁₋₆-alkyl;        and also the possible geometrical and/or isomers, enantiomers        and/or diastereoisomers, tautomers, salts, N-oxides, sulfoxides,        sulfones and metal or metalloid complexes thereof, which are        agriculturally acceptable. Among the compounds defined above,        the most important compounds are the salts, more particularly        the lithium, sodium, potassium or tetraalkyl-ammonium salts.

Among the compounds of formula (Id), the ones that are preferred arethose having one or other of the following characteristics, takenseparately or in combination;

-   -   n represents 2 or 3;    -   B represents a phenylene;    -   D represents a linear, saturated or unsaturated        hydrocarbon-based chain containing from 3 to 17 carbon atoms;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl;        more preferably, those simultaneously having the following        characteristics:    -   n represents 2 or 3;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl;        even more preferably, those simultaneously having the following        characteristics:    -   n represents 2 or 3;    -   D represents a linear, saturated or unsaturated        hydrocarbon-based chain containing from 3 to 17 carbon atoms;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl;        and most preferably those simultaneously having the following        characteristics:    -   n represents 2 or 3;    -   B represents a phenylene;    -   D represents a linear hydrocarbon-based chain containing 11        carbon, which is saturated, or unsaturated between carbons 4 and        5;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl.

Among the compounds of the present invention, the compounds for which Arepresents a methylene group and C represents an oxygen atom are alsomost particularly advantageous, and may be represented by formula (Ie):

in which

-   -   n represents 1, 2 or 3, preferably 2 or 3;    -   B represents        -   an arylene;        -   a heteroarylene comprising 1 or 2 hetero atoms chosen from            nitrogen, oxygen and sulfur;        -   a naphthylene;        -   a heteronaphthylene comprising 1 or 2 hetero atoms chosen            from nitrogen, oxygen and sulfur;        -   a divalent radical derived from 2 fused aromatic rings            containing 5 or 6 atoms each;        -   a divalent radical derived from 2 fused aromatic or            heteroaromatic rings containing 5 or 6 atoms each,            comprising 1 or 2 hetero atoms chosen from nitrogen, oxygen            and sulfur;        -   a biphenylene;        -   or a heterobiphenylene comprising 1 or 2 hetero atoms chosen            from nitrogen, oxygen and sulfur;            these groups possibly being substituted with one or two            substituents R¹² and R¹³ chosen, independently of each            other, from halogen, CN, C(O)OR¹⁴, C(O)NR¹⁵R¹⁶, CF₃, OCF₃,            —NO₂, N₃, OR¹⁴, SR¹⁴, NR¹⁵R¹⁶ and C₁₋₆-alkyl;    -   D represents a linear or branched, saturated or unsaturated        hydrocarbon-based chain containing from 2 to 20 carbon atoms,        preferably a linear hydrocarbon-based chain containing 11        carbons, which is saturated, or unsaturated between carbons 4        and 5;    -   E and G represent, independently of each other, a substituent        chosen from H, OH, OR²⁰, NH₂ and NHR²⁰, preferably NHC(O)CH₃;    -   R¹ represents a substituent chosen from H, C₁₋₆-alkyl, C(O)H and        C(O)CH₃, preferably H or CH₃;    -   R², R³ and R⁶ represent, independently of each other, a        substituent chosen from H, C₁₋₆-alkyl, C(O)C₁₋₆-alkyl,        —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,        —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and        —C(NH)NHC₁₋₆-alkyl; preferably H;    -   R⁴ represents a substituent chosen from H, C₁₋₆-alkyl and R²,        preferably H, C(O)CH₃ or C(O)NH₂;    -   R⁵ represents a substituent chosen from H. C₁₋₆-alkyl, fucosyl        and R²², preferably H;    -   R⁷ represents a substituent chosen from H, C₁₋₆-alkyl,        arabinosyl and R²³, preferably H;    -   R⁸ represents a substituent chosen from H, C₁₋₆-alkyl, fucosyl,        methylfucosyl, sulfofucosyl, acetylfucosyl, arabinosyl, SO₃H,        SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄ and R²⁴, preferably H,        SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄, fucosyl or        methylfucosyl;    -   R⁹ represents a substituent chosen from H, C₁₋₆-alkyl, mannose,        glycerol and R²⁵, preferably H;    -   R¹⁰, R¹¹, R¹⁷ and R¹⁸ represent, independently of each other, a        substituent chosen from C₁₋₆-alkyl and F;    -   R¹⁴, R¹⁵, R¹⁶ and R¹⁹ represent, independently of each other, a        substituent chosen from H, C₁₋₆-alkyl, —C(O)C₁₋₆-alkyl,        —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,        —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and        —C(NH)NHC₁₋₆-alkyl;    -   R²⁰, R²¹, R²², R²³, R²⁴ and R²⁵ represent, independently of each        other, a substituent chosen from C(O)C₁₋₆-alkyl,        —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,        —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and        —C(NH)NHC₁₋₆-alkyl;        and also the possible geometrical and/or optical isomers,        enantiomers and/or diastereoisomers, tautomers, salts, N-oxides,        sulfoxides, sulfones and metal or metalloid complexes thereof,        which are agriculturally acceptable. Among the compounds defined        above, the most important compounds are the salts, more        particularly the lithium, sodium, potassium or        tetraalkylammonium salts.

Among the compounds of (Ie), the ones that are preferred are thosehaving one or other of the following characteristics, taken separatelyor in combination:

-   -   n represents 2 or 3;    -   B represents a phenylene;    -   D represents a linear, saturated or unsaturated        hydrocarbon-based chain containing from 3 to 17 carbon atoms;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or C(O)CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl;        more preferably, those simultaneously having the following        characteristics:    -   n represents 2 or 3;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or C(O)CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl;        even more preferably, those simultaneously having the following        characteristics:    -   n represents 2 or 3;    -   D represents a linear, saturated or unsaturated        hydrocarbon-based chain containing from 3 to 17 carbon atoms;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or C(O)CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl;        and most preferably those simultaneously having the following        characteristics:    -   n represents 2 or 3;    -   B represents a phenylene;    -   D represents a linear hydrocarbon-based chain containing 11        carbons, which is saturated, or unsaturated between carbons 4        and 5;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or C(O)CH₃;    -   R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;    -   R⁴ represents H, C(O)CH₃ or C(O)NH₂;    -   R⁸ represents H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,        fucosyl or methyl-fucosyl.

Among the compounds of formula (I), (Ia), (Ib), (Ic), (Id) or (Ie)according to the invention, the ones that are preferred are those forwhich:

-   -   B represents a substituent chosen from:

B1

B2

B3

B4

B5

B6

B7

B8

B9

B10

B11

B12

B13

B14

B15

B16

B17

B18

B19

B20

-   -   in which R¹² and R¹³ represent two substituents chosen,        independently of each other, from halogen, CN, CF₃, OCF₃, —NO₂,        N₃, OR¹⁴, SR¹⁴, NR¹⁵R¹⁶ and C₁₋₆-alkyl

Among the compounds of formula (I), (Ia), (Ib), (Ic), (Id) or (Ie)according to the invention, the ones that are also preferred are thosefor which

-   -   B represents        -   an arylene;        -   a heteroarylene comprising 1 or 2 hetero atoms chosen from            nitrogen, oxygen and sulfur;        -   a naphthylene;        -   or a heteronaphthylene comprising 1 or 2 hetero atoms chosen            from nitrogen, oxygen and sulfur;    -   10 these groups possibly being substituted with one or two        substituents R¹² and R¹³ chosen, independently of each other,        from halogen, CN, C(O)OR¹⁴, C(O)NR¹⁵R¹⁶, CF₃, OCF₃, —NO₂, N₃,        OR¹⁴, SR¹⁴, NR¹⁵R¹⁶ and C₁₋₆-alkyl;        preferably, those for which    -   B represents        -   an arylene;        -   or a heteroarylene comprising 1 or 2 hetero atoms chosen            from nitrogen, oxygen and sulfur;            these groups possibly being substituted with one or two            substituents R¹² and R¹³ chosen, independently of each            other, from halogen, CN, C(O)OR¹⁴, C(O)NR¹⁵R¹⁶, CF₃, OCF₃,            —NO₂, N₃, OR¹⁴, SR¹⁴, NR¹⁵R¹⁶ and C₁₋₆-alkyl;            more preferably, those for which    -   B represents        -   a phenylene;        -   or a heterophenylene comprising 1 or 2 hetero atoms chosen            from nitrogen, oxygen and sulfur;    -    these groups possibly being substituted with one or two        substituents R¹² and R¹³ chosen, independently of each other,        from halogen, CN, C(O)OR¹⁴, C(O)NR¹⁵R¹⁶, CF₃, OCF₃, —NO₂, N₃,        OR¹⁴, SR¹⁴, NR¹⁵R¹⁶ and C₁₋₆-alkyl;        mention may be made especially of those for which    -   B represents a phenylene B1 that may be substituted with one or        two substituents R¹² and R¹³ chosen, independently of each        other, from halogen, CN, CF₃, OCF₃, —NO₂, N₃, OR¹⁴, SR¹⁴,        NR¹⁵R¹⁶ and C₁₋₆-alkyl.

Among the preferred compounds of the present invention, mention may alsobe made of those having one of the following characteristics, takenseparately or in combination:

-   -   n=2 or 3;    -   A represents —C(O)— or —CH₂—;    -   C represents —O—;    -   E and G represent NHC(O)CH₃;    -   R¹ represents H or C(O)CH₃,    -   R², R³, R⁵, R⁶ and R⁷ represent a hydrogen atom;    -   R⁴ represents a substituent chosen from H, C(O)CH₃ and C(O)NH₂;    -   R⁸ represents a substituent chosen from H, fucosyl,        methylfucosyl, sulfofucosyl, acetylfucosyl, arabinosyl, SO₃H,        SO₃Li, SO₃Na, SO₃K and SO₃N(C₁₋₈alkyl)₄;    -   R⁹ represents a hydrogen atom;        even more preferably, those having the following combination of        characteristics:    -   n=2 or 3;    -   A represents —C(O)— or —CH₂—;    -   C represents —O—;    -   D represents a linear, saturated or unsaturated        hydrocarbon-based chain containing from 7 to 15 carbon atoms;        preferably a hydrocarbon-based chain according to one of the        formulae represented below

D1

D2

D3

D4

D5

D6

in which

-   -   -   m=1 to 12        -   a p=0 to 11        -   q=6 to 14        -   s=5 to 13        -   with m+p≦12 and m+p≧4; even more preferably a            hydrocarbon-based chain according to one of the formulae            represented below

D1

D2

D3

in which

-   -   -   m=1 to 12        -   p=0 to 11        -   q=6 to 14        -   with m+p≦12 and m+p≧4; and most preferably a linear            hydrocarbon-based chain containing 11 carbon atoms, which is            saturated, or unsaturated between carbon atoms 4 and 5;

    -   E and G represent NHC(O)CH₃;

    -   R¹ represents H or C(O)CH₃;

    -   R², R³, R⁵, R⁶ and R⁷ represent a hydrogen atom;

    -   R⁴ represents a substituent chosen from H, C(O)CH₃ and C(O)NH₂;

    -   R⁸ represents a substituent chosen from H, fucosyl,        methylfucosyl, sulfofucosyl, acetylfucosyl, arabinosyl, SO₃H,        SO₃Li, SO₃Na, SO₃K and SO₃N(C₁₋₈alkyl)₄,

    -   R⁹ represents a hydrogen atom;        in particular, the compounds for which R⁸ represents H, SO₃H,        SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄ or a substituent of        formula:

in which

-   -   R²⁶ represents a substituent chosen from H and CH₃, preferably        H;    -   R²⁷ and R²⁸ represent, independently of each other, a        substituent chosen from H, C(O)CH₃, SO₃H, SO₃Li, SO₃Na, SO₃K and        SO₃N(C₁₋₈alkyl)₄, preferably R²⁷ and R²⁸ represent H.

As examples of compounds according to the invention that areparticularly advantageous and preferred, mention may be made of thecompounds corresponding to one of the following formulae:

in which, when it is present, M represents a cation chosen from H⁺, Li⁺,Na⁺, K⁺ and (C₁₋₈alkyl)₄N⁺.

Besides the compounds of the invention that have just been specificallydescribed, the variants of combinations of possible substituents for theformulae (I), (Ia), (Ib), (Ic), (Id) and (Ie) especially, also form partof the invention.

It is known that a chitin oligomer not containing a lipid chain is notactive, and that the degradation of the Nod factors by breaking theamide bond in the rhizosphere thus leads to a loss of activity.

In order to limit, or even prevent, this degradation, a series ofanalogous compounds, some of which are more stable than the natural Nodfactors, was prepared.

II-1. Structure of Compounds According to the Invention

Compounds containing a meta-substituted benzamide group were prepared.It is preferred to keep identical the total number of atoms along thechain (16) and also the unsaturation of cis type in position 9. Inpractice, for the production of the starting materials, the lipid chainmay be linked to the aromatic ring via an oxygen atom.

An analog 4 containing a meta-substituted benzylamine function, and alsoan N-acetylated analog 5, which makes it possible to regain the overallcharge of the natural product, were also synthesized. These analogs wereprepared in the sulfated series.

Two other sulfated analogs, one containing a fully saturated chain andthe other an unsaturated chain of alkyne type, make it possible to studythe effect of the unsaturation of Z type in position 9 present on thenatural product.

Finally, two sulfated analogs, the substitution on the aromatic ring ofwhich is in the ortho position for one and in the para position for theother, make it possible to study the effect of the unsaturation of transtype located in position 2 on the natural product.

Finally, an analog, derived from a fucosyl pentamer, bearing a metasubstitution on the chain, was prepared.

The references for the biological tests are the following compounds:

II-2. Synthesis of the Various Aromatic Chains

For the benzamide LCOs, the coupling with the amino tetramer isperformed with a benzoyl chloride (acylation) and for the benzyl LCOs,with a benzaldehyde (reductive alkylation).

II-2.1. Synthesis of Aromatic Chains Meta-Substituted with theUndec-4Z-Enyloxy Chain

According to the reaction scheme below, the methyl ester 15 is prepared,from which reduction to the aldehyde or saponification to the acid (acylchloride precursor) may be envisaged.

To do this, 1-iodoundec-4Z-ene 13 is used to alkylate methyl3-hydroxybenzoate. The ester 15 is isolated in a yield of 76%.

Conversion of the ester to the aldehyde 17 is performed in two steps.

Moreover, the acyl chloride 19 is obtained by saponification of theester 15 followed by reaction with oxalyl chloride.

II-2.2. Synthesis of Aromatic Chains Meta-Substituted with Undecanyloxyand undec-4-ynyloxy Chains

The same procedure with 1-bromoundecane or 1-iodoundec-4-yne inanhydrous DMF, followed by saponification and formation of the chloride,lead to the acid chlorides 23 and 27.

II-2.3. Synthesis of aromatic chains ortho- or para-substituted with theundec-4Z-enyloxy chain The acid chlorides 31 and 35 are similarlyprepared from 29 and 33, which are obtained as previously by Williamsoncoupling of 1-iodoundec-4Z-ene 13 with methyl 2-hydroxybenzoate 28 (ormethyl salicylate) in a yield of 66%, and with methyl 4-hydroxybenzoate32 in a yield of 79%.

The saponifications and conversions to chloride are quantitative in bothcases.

II-3. N-acylation of the Sulfated Tetramer CO-IV(NH₂, S) with theVarious Benzoyl Chlorides

II-3.1. Coupling with 3-(undec-4Z-enyloxy)benzoyl Chloride 19

The coupling may be performed by dissolving the starting material in aDMF-water mixture in the presence of sodium hydrogen carbonate. Underthese conditions, only the free amine is acylated. With 6 equivalents ofchloride and after reaction for 18 hours, a conversion of about 60% isachieved, but the reaction is highly selective. 33% of desired product 3are thus isolated. The purity of the product is checked by HPLC.

The ultraviolet (UV) absorption spectrum of product 3 is substantiallydifferent from that of the reference compound 12, especially due to thepresence in 3 of an absorption peak at 289 nm. Such a peak, due to thebenzamide group, does not exist for compound 12. This perfectlyillustrates the UV properties of some of the compounds according to theinvention making them easy to assay, in contrast with the natural Nodfactors.

In contrast with compound 12, compound 3 also has a characteristicfluorescence at 345 nm when it is excited at 289 nm.

II-3.2. Coupling with 3-(undecanyloxy)benzoyl Chloride 23 and3-(undec-4-ynyloxy)benzoyl Chloride 27

The same procedure as for the preceding derivative is repeated, i.e.dissolution in a DMF-water mixture and use of several equivalents ofchloride.

Under these conditions, the saturated analog 6 is obtained in a yield of32% (and 47% conversion) and the analog containing a triple bond Z in ayield of 31% (and 70% conversion). The purity is also checked by HPLC.

II-3.3. Coupling with 2-(undec-4Z-enyloxy)benzoyl Chloride 31 and4-(undec-4Z-enyloxy)benzoyl Chloride 35

For these two analogs, by adopting a similar protocol, a yield of 48% isobtained for the ortho-substituted derivative 8 and a yield of 40% isobtained for the para-substituted derivative 9. For the two reactions, 4equivalents of chloride were used. The purity is also checked by HPLC.

II-4. N-Acylation of the Nonsulfated Tetramer CO-IV(NH₂) with3-(undec-4Z-enyloxy)benzoyl Chloride 19

The reaction was carried out as previously in a DMF-water mixture, inwhich the starting material and the chloride are soluble. In order tofacilitate the final purification, the reaction is performed in thepresence of a basic Dowex resin (HCO₃ ⁻).

At the end of the reaction, the reaction medium is diluted with anacetonitrile/water mixture, and the expected compound is purified byfiltration of the resin, passing through acidic Dowex (H⁺), resin,concentration and washing of the solid residue with ethyl acetate andthen with water. 22% of the expected product 2 are thus isolated.

II-5. N-acylation of the Fucosylated Pentamer CO-V(NH₂, Fuc) with3-(undec-4Z-enyloxy)benzoyl Chloride 19

The reaction was performed as for the preceding product, in a DMF-watermixture, in which the starting material and the chloride are soluble. Inorder to facilitate final purification, the reaction is performed in thepresence of a basic Dowex resin (HCO₃ ⁻).

At the end of the reaction, the reaction medium is diluted with anacetonitrile/water mixture, and the expected compound is purified byfiltration of the resin, passage through acidic Dowex resin (H⁺),concentration and washing of the solid residue with ethyl acetate andthen with water. 28% of the expected product 10 are thus isolated.

II-6. Reductive Alkylation of the Sulfated Tetramer with3-(undec-4Z-enyloxy)benzaldehyde

II-6.1. Alkylation of the Tetramer CO-IV(NH₂, S)

The reductive alkylation reaction was performed in anhydrous DMF in thepresence of lithium bromide. With 12 equivalents of aldehyde and 15equivalents of sodium cyanoborohydride, 71% of expected coupling product4 are isolated by chromatography on silica gel after 24 hours.

II-6.2. N-Acetylation of the Coupling Product Obtained from theReductive Alkylation

The reaction is performed in an ethyl acetate-methanol-water mixture byaddition of acetic anhydride, in the presence of sodium hydrogencarbonate. After 12 hours, the starting material 4 is removed by passagethrough H⁺ resin. After purification on silica, the expected product 5is isolated in a yield of 77%. The purity is checked by HPLC.

II-7. Activity Tests

II-7.1. Activity Tests on Temperate Legumes of the Galegoid Group

Temperate legumes of the Galegoid group are nodulated by rhizobia thatproduce Nod factors with the hydrophobic chain having a double bondconjugated to the carbonyl group. This group includes important legumecrops such as alfalfa, pea, broad bean, chickpea and clover.

The sulfated products are tested on alfalfa for induction of theformation of root nodules, and on the model legume Medicago truncatulafor induction of the expression of a symbiotic gene coding for an earlynodulin.

II-7.1.1 Nodulation Tests on Alfalfa

Alfalfa plantlets are grown under axenic conditions in test tubes on anitrogen-poor agar medium (Demont-Caulet et al., Plant Physiol., 120,83-92, 1999). Untreated plantlets serve as control. Natural Nod orsynthetic LCO factors are added at the concentrations indicated.

II-7.1.1.1 Results of Nodulation Tests

The benzamide derivative 3 meta-substituted with the undec-4Z-enyloxychain shows advantageous activity, the activity being similar to that ofthe sulfated tetramer 11 acylated with the reference C16:1Δ9Z chain asshown in FIG. 1.

The benzyl derivative 4 has moderate activity relative to the benzamidederivative 3 as shown in FIG. 2.

Finally, the N-acetylation of the benzyl derivative 4 leads to animprovement in the response, but the activity remains lower than that ofthe benzamide derivative 3 as shown in FIG. 3.

These results indicate the importance of the amide bond. The resultsobtained with these benzamide derivatives confirm the effect of theamide-double bond conjugation present on the natural compound.

The benzamide 7 meta-substitute with the undec-4-ynyloxy chain showsactivity comparable to that of the benzamide derivative 3, whereas thebenzamide compound 6 substituted with the fully saturated chain showsslightly lower activity. These results indicate that an unsaturation inposition 4 may lead to an increase in activity as shown in FIG. 4.

The tests relating to the benzamide derivatives 8 and 9 ortho- andpara-substituted with the undec-4Z-enyloxy chain reveal analogs that areless active than the meta-substituted benzamide derivative 3. The metasubstitution is thus preferred as mimic for an unsaturation of transtype.

II-7.1.2. Tests of Induction of Early Nodulin on Medicago truncatula

These tests are performed to determine whether the synthetic LCOs inducesymbiotic responses by activation on the same signal transductionpathway as the natural Nod factors. The tests are performed on the modellegume Medicago truncatula. The activity of the sulfated benzamidederivative 3, meta-substituted with the undec-4Z-enyloxy chain, which isthe most active synthetic compound in the nodulation test on alfalfa, isstudied on “wild-type” plants and on a mutant in the gene DMI1 which isaltered in the transduction of the Nod factor signal (Catoria et. al.Plant Cell, 12, 1647-1665, 2000). The compound that serves as referenceis the sulfated tetramer 12 acylated with C16:2Δ2E,9Z chain, which is ananalog of the natural Nod factor. The control is the plant cultivated inthe absence of LCO.

II-7.1.2.1 Reporter Gene

It is generally difficult to determine the regulation of expression of aparticular gene, during a biological process, since most of the specificproducts of these genes are not readily detectable or measurable. Toovercome this problem, a technique of fusion with “reporter genes” isused, i.e. genes coding for a readily assayable protein. The fusionconsists in combining the DNA sequence containing the gene regulatoryregions that it is desired to study, with the DNA sequence of thereporter gene. The assembly is then reintroduced into the plant bytransformation. Thus, if the target gene is expressed, the reporter geneis automatically expressed. It is then a matter of assaying the reportergene protein.

In order to avoid a negative interaction with the activity of the plant,reporter genes that do not code for any enzyme normally formed by theplants are used. One of the enzymes most commonly used isβ-glucuronidase (GUS) from Escherichia coli, a hydrolase that catalyzesthe cleavage of a large variety of β-glucuronides. As commercialsubstrate of this enzyme, it is possible to use:

X-Gluc (Sigma B-4782): 5-bromo-4-chloro-3-indolyl glucuronide; the anionformed has a blue color.

II7.1.2.2 Enod11::GUSA

The genes for the legumes involved in modulation may be classified intotwo major types: early nodulin genes (ENOD), which are activated in thefirst days of the infection and activation of the nodulation process;

late nodulin genes, which are not activated until several days after theapplication of the bacteria, and do not intervene until the period ofmaturation of the nodules.

A new gene of Medicago truncatula, MtENOD11, coding for an RPRP(Repetitive proline-rich protein), and transcribed during the firststeps of infection of nodulation on the nodule roots and tissues wasidentified (Journet et al. Mol. Plant-Microbe Interact., 14, 737-748,2001). Using the transgenic Medicago truncatula plant expressing thefusion MtENOD11::GUSA, it is possible to determine whether a Nod factoranalog added to the culture medium of the plant has inducedtranscription of the ENOD11 gene.

For the ENOD11 transcription tests, a Fahraeus medium is used as for themodulation tests, but without agar. The seedlings are placed on paper inpockets containing the culture medium. The responses of two types oftransgenic plants bearing the MtENOD11::GUS: fusion are compared: a“wild-type” (WT) Jemalong plant and a plant bearing a mutation in theDMI1 gene, which is incapable of transducing the Nod factor signal. Theplants are left to grow for 5 days and the plantlets are then treatedwith various concentrations of LCO. After 6 hours, the plantlets areremoved and placed in aqueous medium containing X-Gluc for 1 to 2 hours.The number of roots giving a characteristic blue response is thencounted.

This test is relatively sensitive, to the extent that it is possible towork at LCO concentrations that are lower than those for the modulationtests as shown in FIG. 5.

It is found that the benzamide derivative 3 is approximately 10 timesless active than the reference compound, the acylated tetramer 12.Moreover, as for the reference compound 12, the benzamide derivative 3does not induce any response in the plants bearing the DMI1 mutation. Itmay thus be concluded that the synthetic compound of benzamide typeactivates the transcription of the ENOD11 gene via the same transductionpathway as that activated by the natural Nod factors.

II-7.2 Activity Tests on Other Legumes

Sulfated benzamide derivatives have been shown to have similarbiological activity on the roots of Medicago species than the majornatural sulfated Sinorhizobium meliloti Nod factor which is N-acylatedwith a C16:2 chain. It has been hypothesized that the benzamidederivative is a good structural mimic of the natural S. meliloti Nodfactors having an amide bond between the chitin oligomer backbone andthe hydrophobic chain with a double bond conjugated to the carbonylgroup. This type of alpha-beta conjugated double bond is characteristicof Nod factors from rhizobia that nodulate temperate legumes such asalfalfa, clover, pea, broad bean, chickpea, etc. . . . In contrast,rhizobium that nodulate legumes of tropical origin such as soybean,peanut, bean, cowpea, etc. . . . produce Nod factors in which thecarbonyl group is not conjugated to a double bond. It was thus importantto determine whether a benzamide analog of a natural Nod factor with noconjugated double bond would also exhibit biological activity on thecognate legume.

This question was addressed by using the Lotus corniculatus root hairdeformation bioassay. Lotus corniculatus is a forage crop which isnodulated by rhizobia which produce Nod factors quite similar to thoseproduced by rhizobia which nodulate soybean: the chitin oligomerbackbone has five glucosamine residues, the N-acyl chain is essentiallyvaccenic acid (C18:1) and the reducing glucosamine residue is notsulfated and is O-substituted by a fucosyl residue. Lotus corniculatuswas chosen as a model system because seeds and seedlings are small sizedand convenient to handle.

II-7.2.1 Root Hair Deformation Assay on Lotus corniculatus

Seeds of Lotus corniculatus (cv Rodeo) were sterilized. Germinated seedswith rootlets about 1 cm long were aseptically transferred onto Farhaeussoft agar plates. Plates were sealed with Parafilm and placed verticallyfor two days in a plant growth chamber (at 25° C., with a 16-hr lightperiod, a relative humidity of 75%, OsramVFluora L 77 as the type oflight, and light intensity at the level of the top of the plates of 30μE.m-2.s-1) to allow plant growth and root hair development. Then 2 mlof a Nod factor derivative sterile solution was poured to cover theLotus root system, and after 30 mm, excess liquid was removed. A furtherincubation was performed for 16 hr in the plant growth chamber. Theroots of the five plants were transferred between slide and cover slipand observed by bright field microscopy after staining by methyleneblue.

Hair deformation (Had) activity was estimated by a limit dilutionmethod. Nod factor derivatives were applied at concentrations rangingfrom 10-7 M to 10-11 M. The activity of two DP5 chitin derivatives werecompared, the soybean Nod factor and its benzoylated analog 10. Bothcompounds were O-fucosylated at the reducing end, but differed by theN-substitution on the terminal non-reducing glucosamine residue, eitherC18:1 N-acylated like the soybean Nod factor or N-benzoylated. Eachcompound was dissolved in water/ethanol 50/50; 0,01% Chaps was added ata concentration of 1 mM. These stock solutions were then diluted inwater. To estimate the plant response, a criterion of clear-cut hairbranching was chosen (numerous branching at more than one site on theroot system), and plants exhibiting these pronounced reactions wereclassified as <<<+>>. The statistical significance (at the P=0.05) ofthe proportion of <<+>> responses was calculated using the ratiocomparisons based on the Fisher's <<Exact>> test (SAS software).Experiments were carried out twice. Data are given in the followingTable:

TABLE Root hair deformation assay on Lotus corniculatus 10⁻⁷ M 10⁻⁸ M10⁻⁹ M 10⁻¹⁰ M 10⁻¹¹ M Acylated + + + + − compound Benzoylated + + + − −compound 10

Fifteen plants were used for each treatment and each dilution. Sixty sixuntreated control plants were used to estimate the intrinsic plantvariability for the Hair deformation character. The responses wereclassified “+” when the proportion of Had+ was significantly higher (atthe probability level P=0.05) among the treated plants compared with theuntreated control. Data were analysed using the Fisher's “Exact” test.

These experiments show that the benzamide derivative 10 has a highactivity on the Lotus corniculatus root hair bioassay, with asignificant activity at nanomolar concentration. It may thus beconcluded that benzamide derivatives could be used to stimulatesymbiotic activity on legumes that are nodulated by rhizobia whichproduce Nod factors that have no alpha-beta conjugated double bonds onthe acyl chain, such as soybean.

III EXAMPLES

For the aromatic derivatives, the ring is numbered according to theofficial nomenclature. For the description of the NMR spectra for the COand LCO, the sugars are numbered starting with the reducing end:

The conventional numbering is adopted on each sugar.

2-acetamido-4-O-{2-acetamido-4-O-[2-acetamido-2-deoxy-4-O-(2-deoxy-2-(N-3-(undec-4Z-enyloxy)benzoyl)amino-β-D-glucopyranosyl)-β-D-glucopyranosyl]-2-deoxy-β-D-glucopyranosyl}-2-deoxy-D-glucopyranose(2)

7.2 mg of CO-IV(NH₂) are dissolved in 200 μL of water and 500 μL of DMF,and are then heated to 40° C. 36 mg of Dowex 1×2-100 resin (HCO₃ ⁻) arethen added, followed by addition of 160 μL of a solution of 19 indistilled THF (26 μmol). 108 mg of HCO₃ ⁻ resin and 480 μL of thesolution of 19 in distilled THF (78 μmol) are added in three portionsover 48 hours. The reaction medium is diluted with 3 mL of 1/1acetonitrile/water mixture, the reaction medium is collected, leavingthe resin, and is then filtered through cotton wool to remove theentrained resin beads. The filtrates are passed through a Dowex 50×8-100resin (H⁺) and then concentrated, and washing of the solid residue isthen performed with ethyl acetate, and then with water. 2 mg of a whitepowder are obtained, i.e. a yield of 22%.

¹H NMR (400 MHz, 20/1 DMSO-d6/D₂O) δ (ppm):

7.40−7.31 (m, 3H, ArH-2, ArH-6 and ArH-5), 7.04 (m, 1H, ArH-4),5.41−5.35 (m, 2H, CH=CH), 4.87 (d, 0.7H, J_(1.2)=2.3Hz, H-1α^(I)), 4.52(d, 1H, J=8.3Hz, H-1β^(IV)), 4.42 (d, 0.3H, J=8.0Hz, H ₁-β^(I)), 4.33(2d, 2H, J=8.3Hz, H-1β^(II-III)), 3.98 (t, 2H, J=6.0Hz, ArOCH₂—CH₂).3.78−3.05 (m, 24H, other sugar Hs), 2.16 (dt, 2H, J=5.8 andJ=6.7Hz, CH ₂—CH═CH), 1.97 (dt, 2H, J=6.0 and J=6.2Hz, CH═CH—CH ₂),1.81/1.81/1.79 (3s, 9H, 3 COCH ₃), 1.80−1.72 (m, 2H, ArOCH₂—CH ₂—CH₂),1.28−1.13 (m, 8H, 4 CH ₂), 0.81 (t, 3H, CH ₃, J=6.5Hz).

Mass spectrum:

Positive electrospray (ESI) ionization m/z=1183.5 [M+Na]+

2-acetamido-4-O-{2-acetamido-4-O-[2-acetamido-2-deoxy-4-O-(2-deoxy-2-(N-3-(undec-4Z-enyloxy)benzoyl)amino-β-D-glucopyranosyl)-β-D-glucopyranosyl]-2-deoxy-β-D-glucopyranosyl}-2-deoxy-6-O-sulfo-D-glucopyranose,sodium salt (3)

15 mg of CO-IV(NH₂,S) (17 μmol) are dissolved in 100 μL of water and 250μL of DMF. 3 mg of sodium hydrogen carbonate (34 μmol) are then added,followed by addition of 20 μL of a solution of 19 in THF at aconcentration of 0.25 g/mL (16.4 μmol). The reaction medium is heated to60° C. and 100 μL of the solution of 48 and 10 mg of sodium hydrogencarbonate are added in six portions over 18 hours. After concentrating,the residue is purified by placing it in dichloromethane(DCM)/methanol(5/1) on a column of silica, while diluting it greatly, in order toremove the lipid chain. The elution is then performed with E/M/W (7/2/1Ethyl acetate/Methanol/Water). 6.5 mg of a white solid are thusisolated, i.e. a yield of 33%.

¹H NMR (400 MHz, DMSO-CD₃OD (1/2)) δ(ppm):

7.48 and 7.41 (m, 2H, ArH-2 and ArH-6), 7.36 (dd, 1H, ArH-5, J_(5.6)7.7Hz and J_(5.4) 8.1Hz), 7.07 (ddd, 1H, ArH-4, J_(4.2)≈J_(4.6) 1.4Hz),5.41 (m, 2H, CH═CH), 5.03 (d, 0.8H, H-1α^(I), J_(1*a*,2) 3.2Hz),4.68−4.59−4.50 (3 d, 3H, H-1β^(II,III,IV), J_(1β.2) 8.4Hz, 8.5Hz and8.7Hz), 4.56 (d, 0.2H, H-1β^(I), J_(1β.2) 7.7Hz), 4.25−3.30 (m, 26H, CH₂—OAr, other Hs of the sugars), 2.25 (td, 2H, CH ₂—CH═CH—CH₂, J 6.7Hzand J 6.2Hz), 2.10−1.90 (m, 11H, CH₂—CH═CH—CH ₂ and 3 CH ₃CO), 1.83 (tt,2H, ArO—CH₂—CH ₂—CH₂, J 6.7Hz), 1.35−1.20 (m, 8H, 4 CH ₂), 0.88 (m, 3H,CH ₃)

Mass spectrum:

Negative ESI m/z=1139.4 [M-Na−]

UV: 289 nm

Fluorescence: λ_(ex): 289 nm; λ_(em): 345 nm

2-acetamido4-O-{2-acetamido-4-O-[2-acetamido-2-deoxy-4-O-(2-deoxy-2-(N-3-(undec-4Z-enyloxy)benzyl)amino-β-D-glucopyranosyl)-β-D-glucopyranosyl]-2-deoxy-β-D-glucopyranosyl}-2-deoxy-6-O-sulfo-D-glucopyranose,sodium salt (4)

11 mg of CO-IV(NH₂,S) (12 μmol) are dissolved in 0.5 mL of DMF to whichare added 12 mg of lithium bromide. 2 mg of sodium cyanoborohydride (32μmol) and 100 μL of a solution of 17 in THF at a concentration of 73mg/mL (26 μmol) are added. The reaction medium is heated at 40° C. for 4hours. Every 2 hours, 2 equivalents of aldehyde and 2.5 equivalents ofsodium cyanoborohydride are added, i.e. in total 12 equivalents ofaldehyde and 15 equivalents of sodium cyanoborohydride. Although theconversion is not complete, the reaction is stopped by destroying theexcess sodium cyanoborohydride with 0.5 N hydrochloric acid. When theevolution of gas has ended, the medium is diluted in water andfreeze-dried. The resulting material is taken up in water, 5 mg ofsodium hydrogen carbonate (59 μmol) are added to return to basic pH, andthe resulting material is then coevaporated twice with methanol. Theresidual white solid is placed in DCM/methanol (5/1) on a column ofsilica, while diluting it greatly, in order to remove the lipid chain.The elution is then performed with EIM/W (5/2/1) and then (4/1/1). 10 mgof white needles are thus isolated, i.e. a yield of 71%.

¹H NMR (400 MHz, DMSO-CD₃OD (2/1)) δ (ppm):

7.31 (dd, 1H, ArH-5, J_(4.5) 8.2Hz and J_(5.6) 7.8Hz), 7.02 (m, 2H,ArH-2 and ArH-6), 6.90 (dd, 1H, ArH-4, J_(4.6) 2.3Hz), 5.51 (m, 2H,CH═CH), 5.08 (d, 0.8H, H-1α^(I), J_(1α.2) 3.1Hz), 4.67 (m, 2.2H,H-1β^(I,II,III)), 4.47 (d, 1H, H-1β^(IV), J_(1β.2) 8.0Hz), 4.06 (t, 2H,CH ₂—OAr, J 6.3Hz), 3.94 (s, 2H, NH—CH ₂—Ar), 4.25−3.45 (m, 23H, otherHs of the sugars), 2.45 (dd, 1H, H ₂ ^(IV), J_(1β.2)≈J_(2.3) 8.8Hz),2.31−2.12 (2 m, 4H, CH ₂—CH═CH—CH ₂), 2.07−2.04−2.01 (3 s, 9H, 3 CH₃CO), 1.89 (tt, 2H, ArO—CH₂—CH ₂—CH₂—CH═CH, J 6.9Hz), 1.45−1.25 (m, 8H,4 CH₂), 0.97 (t, 3H, CH ₃, J 6.8Hz)

¹³C NMR (50 MHz, DMSO-CD₃OD (2/1)) δ (ppm):

172 (3 CH₃ CO), 160 (ArC-3), 132−131−130 (ArC-1, ArC-5, CH═CH), 122(ArC-6), 115 (ArC-2, ArC-4), 105 (C-1β^(II,III,IV)), 98 (C-1β^(I)), 92(C-1α^(I)), 82−53 (21 C of the sugars and Ar—CH₂—NH), 68 (CH₂—OAr),33-23 (10 CH₂ and 3 CH₃CO), 14 (CH₃)

Mass spectrum:

Negative ESI m/z=1125.4 [M-Na]−

2-acetamido-4-O-{2-acetamido-4-O-[2-acetamido-2-deoxy-4-O-(2-deoxy-2-(N-3-(undec-4Z-enyloxy)benzyl)acetamido-β-D-glucopyranosyl)-β-D-glucopyranosyl]-2-deoxy-β-D-glucopyranosyl}-2-deoxy-6-O-sulfo-D-glucopyranose,sodium salt (5)

20 mg of sodium hydrogen carbonate and 15 μL of acetic anhydride areadded to a solution of 13 mg of 4 (11 μmol) in 0.3 mL of E/M/W (1/1/1).The reaction medium is stirred at room temperature for 12 hours. Afterconcentrating, the residual oil is taken up in E/M/W (1/1/1) and Dowex50×8−100H+ resin is added. The mixture is filtered and Amberlite IR120Na+ resin is added to the filtrate. After filtering and concentrating,the product is purified by chromatography in E/M/W (4/1/1). 10 mg of awhite solid are thus isolated, i.e. a yield of 77%.

¹H NMR (400 MHz, DMSO-CD₃OD (2/1)) δ (ppm):

7.25−7.18 (2 t, 1H, ArH-5, J_(5.4) 7.8Hz and J_(5.6) 7.9Hz), 7.10−6.85(m, 2H, ArH-2 and ArH-6), 6.82−6.75 (2 d, 1H, ArH-4), 5.40 (m, 2H,CH═CH), 5.06 (d, 0.6H, H-1α^(I), J_(1α. 2) 3.4Hz), 4.75−4.35 (m, 3.4H,H-1β^(I,II,III,IV)), 4.30−4.05 (m, 2H, H-6a,b^(I)), 4.00−3.30 (m, 25H,other Hs of the sugars and CH ₂—OAr), 3.80 (s, 2H, NAc-CH ₂—Ar), 2.90(m, 1H, H-2^(IV)), 2.23−2.03 (2 m, 4H, CH ₂—CH═CH—CH ₂), 1.99−1.90 (m,12H, CH ₃CO), 1.80 (tt, 2H, ArO—CH₂—CH ₂—CH₂—CH═CH, J 6.9 Hz), 1.35−1.20(m, 8H, 4 CH ₂), 0.87 (m, 3H, CH ₃)

¹³C NMR (50 MHz, DMSO-CD₃OD (2/1)) δ (ppm):176 (CH₃ CON), 174−173−173 (3CH₃ CO), 161 (ArC-3), 141 (ArC-1), 132−130−129−127 (ArC-2, ArC-4, ArC-5,ArC-6, CH═CH), 103 (3 C-1β^(I,II,IV)), 100 (C-1β^(I)), 92 (C-1α^(I)),82−50 (24 C of the sugars, Ar—CH₂—NH and CH₂—OAr), 33−23 (10 CH₂ and 3CH₃CO), 14 (CH₃)

Mass spectrum: Negative ESI m/z=1067.4 [M-Na]−

2-acetamido-4-O-{2-acetamido-4-O-[2-acetamido-2-deoxy-4-O-(2-deoxy-2-(N-3-(undecanyloxy)benzoyl)amino-β-D-glucopyranosyl)-2-deoxy-β-D-glucopyranosyl]-β-D-glucopyranosyl}-2-deoxy-6-O-sulfo-D-glucopyranose,sodium salt (6)

15 mg of CO-IV(NH₂,S) (17 μmol) are dissolved in 100 μL of water and 250μL of DMF. 6 mg of sodium hydrogen carbonate (71 μmol) and then 25 μL ofa solution of 23 in THF at a concentration of 210 mg/mL (17 μmol) arethen added. The reaction medium is heated to 60° C. and 200 μL of thesolution of chloride and 16 mg of sodium hydrogen carbonate are added ineight portions over 24 hours. After concentrating, the residue ispurified by placing it in DCM/methanol (5/1) on a column of silica,while diluting it greatly, in order to remove the lipid chain. Theelution is then performed with E/M/W (4/1/1). 6.3 mg of a white solidare thus isolated, i.e. a yield of 32%.

¹H NMR (400 MHz, DMSO-CD₃OD (1/3)) δ (ppm):7.44 (m, 2H, ArH-2 andArH-6), 7.39 (dd, 1H, ArH-5, J_(5.4)≈J_(5.6) 7.9Hz), 7.10 (ddd, 1H,ArH4, J_(4.6)≈J_(4.2) 2.1Hz), 5.05 (d, 0.7H, H-1α^(I), J_(1α.2) 3.0Hz),4.70−4.40 (m, 3.3H, H-1β^(I,II,III,IV)), 4.22 (m, 1H, H-6a^(I)),4.10−3.20 (m, 24H, CH ₂—OAr and other Hs of the sugar), 2.03−1.99−1.96(3 s, 9H, CH ₃CO), 1.80 (m, 2H, ArO—CH₂—CH ₂—CH₂), 1.35−1.25 (m, 8H, 4CH ₂), 0.92 (t, 3H, CH ₃, J 6.5Hz)

Mass spectrum: Negative ESI m/z=1141.5 [M-Na]−

2-acetamido-4-O-{2-acetamido-4-O-[2-acetamido-2-deoxy-4-O-(2-deoxy-2-(N-3-(undec-4Z-ynyloxy)benzoyl)amino-β-D-glucopyranosyl)-β-D-glucopyranosyl]-2-deoxy-β-D-glucopyranosyl}-2-deoxy-6-O-sulfo-D-glucopyranose,sodium salt (7)

14 mg of CO-IV(NH₂,S) (16 μmol) are dissolved in 100 μL of water and 250μL of DMF. 5 mg of sodium hydrogen carbonate (60 μmol) and then 25 μL ofa solution of 27 in THF at a concentration of 190 mg/mL (16 μmol) arethen added. The reaction medium is heated to 60° C. and 200 μL of thesolution of chloride and 16 mg of sodium hydrogen carbonate are added ineight portions over 24 hours. After concentrating, the residue ispurified by placing it in DCM/methanol (5/1) on a column of silica,while diluting it greatly, in order to remove the lipid chain. Theelution is then performed with E/M/W (4/1/1). 5.7 mg of expected productare thus isolated in the form of a white solid, i.e. a yield of 31%.

¹H NMR (400 MHz, DMSO-CD₃OD (1/2)) δ (ppm):7.43 (m, 2H, ArH-2 andArH-6), 7.37 (dd, 1H, ArH-5, J_(5.4) 8.1Hz and J_(5.6) 8.0Hz), 7.10(ddd, 1H, ArH-4, J_(4.2)≈J_(4.6) 2.0Hz), 5.04 (d, 0.7H, H-1α^(I),J_(1α.2) 3.3Hz), 4.65−4.59 (2 d, 2H, H-1β^(II,III), J_(1β.2) 28.4Hz andJ_(1β.2) 8.5Hz), 4.54 (d, 0.3H, H-1β^(I), J_(1α.2) 7.9Hz), 4.49 (d, 1H,H-1β^(IV), J_(1β.2) 8.7Hz), 4.23 (dd, 1H, H-6a^(I), J_(6a.6b) 11.1Hz andJ_(6a.5) 3.7Hz), 4.12 (t, 2H, CH ₂—OAr, J 6.2Hz), 4.10−3.40 (m, 21H,other Hs of the sugars), 2.35−2.13 (2 m, 4H, CH ₂—C≡C—CH ₂),2.02−1.98−1.96 (3 s, 9H, 3 CH ₃CO), 1.92 (m, 2H, ArO—CH₂—CH ₂—CH₂),1.45−1.25 (m, 8H, 4 CH ₂), 0.88 (t, 3H, CH ₃, J 6.7Hz)

¹³C NMR (62.5 MHz, DMSO-CD₃OD (1/2)) δ (ppm):

173 (3 CH₃ CO), 170 (NCOAr), 158 (ArC-3), 137 (ArC-1), 131 (ArC-5), 121(ArC-6), 119 (ArC-4), 115 (ArC-2), 103 (C-1β^(II,III,IV)), 96(C-1β^(I)), 92 (C-1α^(I)), 82−50 (20 C of the sugars, C≡C and CH₂—OAr),33−16 (7 CH₂ and 3 CH₃CO), 15 (CH₃)

Mass spectrum:

Negative ESI m/z=1137.1 [M-Na]−

2-acetamido-4-O-{2-acetamido-4-O-[2-acetamido-2-deoxy-4-O-(2-deoxy-2-(N-2-(undec-4Z-enyloxy)benzoyl)amino-β-D-glucopyranosyl)-β-D-glucopyranosyl]-2-deoxy-β-D-glucopyranosyl}-2-deoxy-6-O-sulfo-D-glucopyranose,sodium salt (8)

10 mg of CO-IV(NH₂,S) (11 μmol) are dissolved in 100 μL of water and 250μL of DMF. 2 mg of sodium hydrogen carbonate (24 μmol) and then 15 μL ofa solution of 31 in THF at a concentration of 115 mg/mL (6 μmol) arethen added. The reaction medium is heated to 60° C. and 105 μL of thesolution of chloride and 6 mg of sodium hydrogen carbonate are added inseven portions over 18 hours. After concentrating, the residue ispurified by placing it in DCM/methanol (5/1) on a column of silica,while diluting it greatly, in order to remove the lipid chain. Theelution is then performed with E/M/W (9/2/1). 6.2 mg of a white solidare thus isolated, i.e. a yield of 48% (but a conversion of only 50%).

¹H NMR (400 MHz, DMSO-CD₃OD (1/2)) δ (ppm):

7.99 (dd, 1H, ArH-6, J_(6.5) 7.5Hz and J_(6.4) 1.8Hz), 7.55 (ddd, 1H,ArH-4, J_(4.3) 8.3Hz and J_(4.5) 7.8Hz), 7.20 (d, 1H, ArH-3), 7.10 (dd,1H, ArH-5), 5.52 (m, 2H, CH═CH), 5.06 (d, 0.7H, H-1α^(I), J_(1α.2)3.0Hz), 4.70−4.60−4.53 (4 d superimposed, 3.6H, H-1β^(I,II,II, IV))4.20−3.40 (m, 25H, other Hs of the sugars and CH ₂—OAr), 2.33−2.11 (2 m,4H, CH ₂—CH═CH—CH ₂), 2.03−2.01−2.00 (3 s, 9H, 3 CH ₃CO), 2.05 (m, 2H,ArO—CH₂—CH ₂—CH₂), 1.50−1.20 (m, 8H, 4 CH ₂), 0.94 (t, 3H, CH ₃, J6.8Hz)

¹³C NMR (62.5 MHz, DMSO-CD₃OD (1/2)) δ (ppm):

172 (3 CH₃ CO), 171 (NCOAr), 158 (ArC-1), 133 (ArC-4, CH═CH), 129(ArC-6), 122 (ArC-5,), 114 (ArC-3), 103 (C-1β^(II,III,IV)), 96(C-1β^(I)), 92 (C-1α^(I)), 82-50 (all the other Cs of the sugars andCH₂OAr), 33−24 (7 CH₂ and 3 CH₃CO), 15 (CH₃)

Mass spectrum:

Negative ESI m/z=1139.5 [M-Na]−

2-acetamido-4-O-{2-acetamido-4-O-[2-acetamido-2-deoxy-4-O-(2-deoxy-2-(N-4-(undec-4Z-enyloxy)benzoyl)amino-β-D-glucopyranosyl)-β-D-glucopyranosyl]-2-deoxy-β-D-glucopyranosyl}-2-deoxy-6-O-sulfo-D-glucopyranose,sodium salt (9)

10 mg of CO-IV(NH₂,S) (11 μmol) are dissolved in 100 μL of water and 250μL of DMF. 2 mg of sodium hydrogen carbonate (24 μmol) and then 15 μL ofa solution of 35 in THF at a concentration of 115 mg/mL (6 μmol) arethen added. The reaction medium is heated to 60° C. and 105 μL of thesolution of chloride and 6 mg of sodium hydrogen carbonate are added inseven portions over 17 hours. After concentrating, the residue ispurified by placing it in DCM/methanol (5/1) on a column of silica,while diluting it greatly, in order to remove the lipid chain. Theelution is then performed with E/M/W (9/2/1). 5.2 mg of a white solidare thus isolated, i.e. a yield of 40% (but a conversion of only 60%).

¹H NMR (400 MHz, DMSO-CD₃OD (1/2)) δ (ppm):

7.89 (d, 2H, ArH-2 and ArH-6, J_(2.3)≈J_(6.5) 8.8Hz), 7.04 (d, 2H, ArH-3and ArH-5), 5.48 (m, 2H, CH═CH), 5.05 (d, 0.6H, H-1α^(I), J_(1α.2)3.1Hz), 4.69−4.55−4.50 (4 d superimposed, 3.6H, H-1β^(I,II,III,IV)),4.30−3.40 (m, 23H, other Hs of the sugars), 4.10 (t, CH ₂—OAr, J 6.3Hz),2.28−2.09 (2 m, 4H, CH ₂—CH═CH—CH ₂), 2.02−1.99−1.97 (3 s, 9H, 3 CH₃CO), 1.89 (m, 2H, ArO—CH₂—CH ₂—CH₂), 1.45−1.25 (m, 8H, 4 CH ₂), 0.93(t, 3H, CH ₃, J 7.0Hz)

¹³C NMR (62.5 MHz, DMSO-CD₃OD (1/2)) δ (ppm):

172 (3 CH₃ CO), 169 (NCOAr), 163 (ArC-1), 132−130−129 (ArC-2, ArC-6,CH═CH), 115 (ArC-3, ArC-5), 103 (C-1β^(II,III,IV)), 97 (C-1β^(I)), 92(C-1α^(I)), 83−50 (all the other Cs of the sugars and CH₂OAr), 33−23 (7CH₂ and 3 CH₃CO), 15 (CH₃)

Mass spectrum:

Negative ESI m/z=1139.5 [M-Na]−

2-acetamido-4-O-[2-acetamido-4-O-{2-acetamido-4-O-[2-acetamido-2-deoxy-4-O-(2-deoxy-2-(N-3-(undec-4Z-enyloxy)benzoyl)amino-β-D-glucopyranosyl)-β-D-glucopyranosy]-2-deoxy-β-D-glucopyranosyl}-2-deoxy-β-D-glucopyranosyl]-2-deoxy-6-O-(-α-L-fucopyranosyl)-D-glucopyranose(10)

The fucosyl pentamer CO-V(NH₂, Fuc) (7.3 mg, 6.4 μmol) is dissolved inH₂O (140 μL), followed by addition of DMF (350 μL) and the mixture isbrought to 30° C. Dowex 1x2-100 resin (HCO₃ ⁻) is then added, followedby addition of a solution (THF, 110 μL) of the acid chloride 19 (6 mg).The reaction mixture is stirred for 24 hours, during which time threefurther additions of resin and of acid chloride solution are made. Thereaction medium is then diluted in H₂O/CH₃CN (1/1, 2 mL), heated to 56°C., and the supernatant is then filtered through cotton wool. The resinbeads and the walls of the flask are extracted several times at 56° C.with H₂O/CH₃CN (4/1, 7/3, 3/2, 1/1, 2/3, 3/7 and 1/4, 2 mL each). Thevarious fractions are passed through a Dowex 50x8-100 resin (H⁺), andthen pooled and concentrated. The residue is successively washed withEtOAc (3×1 mL) and then H₂O (3×1 mL), and then redissolved in H₂O/CH₃CN(1/1, 10 mL) by heating to 56° C., and then by sonication. The solutionis then freeze-dried, and the expected product is obtained in the formof a white powder (2.5 mg, 28%).

The starting material retained on the acid resin is then eluted (2.3 mg,31%) using aqueous ammonia solution (H₂O, 2%).

¹H NMR (400 MHz, DMSO-d₆/D₂O 20/1) δ (ppm):

7.43−7.30 (m, 3H, ArH-2, ArH-6 and ArH-5); 7.05 (m, 1H, ArH-4);5.45−5.32 (m, 2H, CH═CH); 4.84 (d, 0.8H, J_(1.2)=1.9Hz, H-1α^(I)); 4.66(d, 0.8H, J_(1.2)<1.0Hz, H-1Fuc-GIcNAcα), 4.65 (d, 0.2H, J_(1.2)<1.0Hz,H-1Fuc-GlcNAcβ), 4.52 (d, H, J=8.5Hz, H-1β^(IV)), 4.45/4.35/4.33 (4d,4H, J=8.5Hz, H-1β^(II-IV) _(),) 4.42 (d, 0.2H, J=7.0Hz, H-1β^(I)); 3.99(t, 2H, J=6.1Hz, ArOCH ₂—CH₂), 3.88 (dt, 1H, H-5Fuc), 3.78−3.05 (m, 33H,other sugar Hs), 2.17 (dt, 2H, J=6.0 and J=6.8Hz, CH ₂—CH═CH), 1.99 (dt,2H, J=5.9 and J=6.2Hz, CH═CH—CH ₂), 1.82/1.81/1.81/1.79 (4s, 12H, 4 COCH₃), 1.80−1.72 (m, 2H, ArOCH₂—CH ₂), 1.31−1.15 (m, 8H, 4 CH ₂), 1.08 (d,0.6H, J_(5.6)=6.9Hz, H-6Fuc-GIcNAcβ), 1.05 (d, 2.4H, J_(5.6)=6.5Hz,H-6Fuc-GlcNAcα), 0.82 (t, 3H, CH ₃, J=6.5Hz).

methyl 3-(undec-4Z-enyloxy)benzoate (15)

850 mg of 14 (6.15 mmol) and 900 mg of K₂CO₃ (6.51 mmol) are added to1.7 g of 13 (6.07 mmol) in anhydrous DMF (20 mL). After reaction for 4hours at 90° C., the reaction medium is concentrated, taken up in DCMand then washed with water. 1.87 g of a yellow oil are obtained, and arechromatographed on silica gel in pentane/ethyl acetate (50/1). 1.37 g ofa yellow oil are isolated, i.e. a yield of 76%.

¹H NMR (250 MHz, CDCl₃) δ (ppm):

7.60 (ddd, 1H, ArH-6, J_(6.5) 8.0Hz and J_(6.4)=J_(6.2) 0.5Hz), 7.52(dd, 1H, ArH-2, J_(2.4) 3.0Hz), 7.31 (dd, 1H, ArH-5, J_(5.4) 8.0Hz),7.07 (ddd, 1H, ArH-4), 5.38 (m, 2H, CH═CH), 3.98 (t, 2H, CH ₂—OAr, J6.3Hz), 3.89 (s, 3H, OCH ₃), 2.22−1.99 (2 m, 4H, CH ₂—CH═CH—CH ₂), 1.83(tt, 2H, ArO—CH₂—CH ₂—CH₂—CH═CH, J 6.8Hz), 1.55−1.20 (m, 8H, 4 CH ₂),0.84 (t, 3H, CH ₃, J 7.5Hz)

¹³C NMR (62.5 MHz, CDCl₃) δ (ppm):

131−129−128 (C-5, CH═CH), 122 (C-6), 120 (C-4), 115 (C-2), 66 (CH₂—OAr),52 (CH₃O), 32−22 (7 CH₂), 14 (CH₃)

Mass spectrum:

Positive ESI m/z=327.2 [M+Na]+

High res. Calc. for C₁₉H₂₈O₃Na: 327.193614, Found: 327.193200

Elemental analysis:

Calc. Found C 74.96 74.68 H 9.27 9.37 O 15.77 15.79

Infrared (cm⁻¹): 2970-2950-2927-2858-1726-1586-1446-1288-1228-756

3-(undec-4Z-enyloxy)benzyl alcohol (16)

35 mg of lithium aluminum hydride (922 μmol) are added, at 0° C., to 140mg of 15 (460 μmol) in ether (3 mL). After reaction for 1 hour 30minutes, the reaction medium is diluted with ether and hydrolyzed withtwo drops of water. After filtering through Celite, drying over Na₂SO₄and concentrating, 127 mg of a colorless oil are isolated, i.e. a yieldof 99%.

¹H NMR (250 MHz, CDCl₃) δ (ppm):

7.18 (dd, 1H, ArH-5, J_(5.6) 8.0Hz and J_(5.4) 8.3Hz), 6.84 (m, 2H,ArH-2 and ArH-4), 6.75 (dd, 1H, ArH-4, J_(4.2) 2.9Hz), 5.32 (m, 2H,CH═CH), 4.58 (s, 2H, CH ₂OH), 3.89 (t, 2H, CH ₂—OAr, J 6.3 Hz),2.16−1.95 (2 m, 4H, CH ₂—CH═CH—CH ₂), 1.76 (tt, 2H, ArO—CH₂—CH₂—CH₂—CH═CH, J 6.8 Hz), 1.45−1.18 (m, 8H, 4 CH ₂), 0.84 (t, 3H, CH ₃, J6.3Hz)

¹³C NMR (62.5 MHz, CDCl₃) δ (ppm):

159 (C-3), 142 (C-1), 131−130−128 (C-5, CH═CH), 119 (C-6), 114 (C-4),113 (C ₂), 67 (CH₂—OAr), 65 (CH₂OH), 32−23 (7 CH₂), 14 (CH₃)

Mass spectrum:

Positive ESI m/z=299.2 [M+Na]+

High res. Calc. for C₁₈H₂₈O₂Na: 299.198700, Found:299.199250

Infrared (cm⁻¹): 3329, 3005, 2940, 2925, 2855, 1669, 1602, 1452, 1264

3-(undec-4Z-enyloxy)benzaldehyde (17)

10 mL of anhydrous DCM and then 190 mg of PCC (881 μmol) are added underargon to 120 mg of alcohol 16 (434 μmol) dried by coevaporation withtoluene. The reaction is heated to the reflux point of the DCM for 1hour. After cooling, the reaction medium is diluted with ether andfiltered through Florisil. After concentrating, 118 mg of a yellow oilare obtained, i.e. a yield of 99%.

¹H NMR (250 MHz, CDCl₃) δ (ppm):

9.95 (s, 1H, CHO), 7.42 (m, 2H, ArH-6 and ArH-5), 7.36 (d, 1H, ArH-2,J_(2.4) 2.9Hz), 7.15 (m, 1H, ArH-4), 5.39 (m, 2H, CH═CH), 3.99 (t, 2H,CH ₂—OAr, J 6.3Hz), 2.21−1.99 (2 m, 4H, CH ₂—CH═CH—CH ₂), 1.84 (tt, 2H,ArO—CH₂—CH ₂—CH₂—CH═CH, J 6.8Hz), 1.40−1.15 (m, 8H, 4 CH ₂), 0.84 (t,3H, CH ₃, J 6.6Hz)

¹³C NMR (62.5 MHz, CDCl₃) δ (ppm):

192 (CHO), 160 (C-3), 138 (C-1), 131−130−128 (C-5, CH═CH), 123 (C-6),122 (C-4), 113 (C-2), 67 (CH₂—OAr), 52 (CH₃O), 32−23 (7 CH₂), 14 (CH₃)

Mass spectrum:

Chemical ionization (CI) 1% solution in DCM

A fine desorption peak

M+1=275

Infrared (cm⁻¹): 3005-2940-2927-2855-2723-1700-1599-1452-1263-787

3-(undec-4Z-enyloxy)benzoic acid (18)

4 mL of 1 N sodium hydroxide solution (4.0 mmol) are added portionwiseto 1.14 g of 15 (3.74 mmol) in methanol (30 mL). The solution isrefluxed overnight. A further 4 mL of 1 N sodium hydroxide solution areadded, and the mixture is refluxed for a further 1 hour 30 minutes.After evaporating off the solvent, the reaction medium is acidified with0.5 N HCl and extracted with DCM. 1.04 g of a yellow oil are obtained,i.e. a yield of 96%.

¹H NMR (200 MHz, CDCl₃) δ (ppm):

10.00−9.00 (bd, 1H, CO₂ H), 7.69 (d, 1H, ArH-6, J_(6.5) 7.8Hz), 7.60 (d,1H, ArH-2, J_(2.4) 2.4Hz), 7.35 (dd, 1H, ArH-5, J₅₄ 8.3Hz), 7.14 (dd,1H, ArH-4), 5.40 (m, 2H, CH═CH), 4.00 (t, 2H, CH ₂—OAr, J 6.3Hz),2.21−2.00 (2 m, 4H, CH ₂—CH═CH—CH ₂), 1.85 (tt, 2H, ArO—CH₂—CH₂—CH₂—CH═CH, J 6.8Hz), 1.35−1.05 (m, 8H, 4 CH ₂), 0.85 (t, 3H, CH ₃, J6.5Hz)

¹³C NMR (50 MHz, CDCl₃) δ (ppm):

172 (CO₂H), 159 (C-3), 131−130−130−128 (C-1, C-5, CH═CH), 121-122 (C-4,C-6), 115 (C-2), 67 (CH₂—OAr), 32−23 (7 CH₂), 14 (CH₃)

Mass spectrum:

Negative ESI m/z=289.1 [M-H]−

High res. Calc. for C₁₈H₂₅O₃: 289.180370, Found: 289.180730

Elemental analysis:

Calc. Found C 74.45 74.29 H 9.02 9.01

Infrared (cm⁻¹): 2970-2950-2925-2854-1695-1585-1286-757

3-(undec-4Z-enyloxy)benzoyl chloride (19)

1 mL of oxalyl chloride (11.5 mmol) and two drops of anhydrous DMF areadded under argon to 100 mg of toluene-dried 18 (345 μmol) dissolved in20 mL of anhydrous DCM. The medium is stirred at room temperature fortwo hours, and then concentrated to give 106 mg of the expected chloridein the form of a yellow oil, i.e. a yield of 99%.

¹H NMR (250 MHz, CDCl₃) δ (ppm):

7.71 (ddd, 1H, ArH-6, J_(6.5) 8.3Hz, J_(6.4) 2.4Hz and J_(6.2) 0.9Hz),7.57 (dd, 1H, ArH-2, J_(2.4) 1.6Hz), 7.39 (dd, 1H, ArH-5, J_(5.4)8.3Hz), 7.20 (ddd, 1H, ArH-4), 5.40 (m, 2H, CH═CH), 3.99 (t, 2H, CH₂—OAr, J 6.3Hz), 2.23−2.00 (2 m, 4H, CH ₂—CH═CH—CH ₂), 1.85 (tt, 2H,ArO—CH₂—CH ₂—CH₂—CH═CH, J 7.0Hz), 1.28−1.15 (m, 8H, 4 CH ₂), 0.85 (t,3H, CH ₃, J 6.5Hz)

methyl 3-(undecyloxy)benzoate (21)

350 mg of 14 (2.30 mmol) and 330 mg of K₂CO₃ (2.39 mmol) are added to554 mg of 1-bromoundecane (2.35 mmol) in anhydrous DMF (7 mL). Afterreaction for 16 hours at 90° C., the reaction medium is concentrated,taken up in DCM and then washed with water. 607 mg of a yellow oil areobtained, and are chromatographed on silica gel in pentane/ethyl acetate(60/1). 579 mg of expected coupling product are isolated in the form ofa yellow oil, i.e. a yield of 82%.

¹H NMR (200 MHz, CDCl₃) δ (ppm):

7.62 (m, 1H, ArH-6), 7.55 (m, 1H, ArH-2), 7.34 (dd, 1H, ArH-5, J₅₄ 8.1Hzand J_(5.6) 7.7Hz), 7.10 (ddd, 1H, ArH-4, J_(4.6) 2.8Hz and J_(4.2)0.8Hz), 4.00 (t, 2H, CH ₂—OAr, J 6.6Hz), 3.92 (s, 3H, OCH ₃), 1.80 (tt,2H, ArO—CH₂—CH ₂-CH₂, J 6.6Hz and J 6.4Hz), 1.52−1.20 (m, 16H, 8 CH ₂),0.89 (t, 3H, CH ₃, J 6.7Hz)

¹³ CNMR (62.5 MHz, CDCl₃) δ (ppm):

167 (CO₂ CH₃), 159 (C-3), 131 (C-1), 129 (C-5), 122 (C-6), 120 (C-4),115 (C-2), 68 (CH₂—OAr), 52 (CH₃O), 32−23 (9 CH₂), 14 (CH₃)

Mass spectrum:

Positive ESI m/z=329.2 [M+Na]+

High res. Calc. for C₁₉H₃₀O₃Na: 329.209264, Found: 329.207940

Infrared (cm⁻¹): 2950-2925-2854-1727-1586-1446-1287-1228-756

3-(undecyloxy)benzoic acid (22)

600 μL of 1 N sodium hydroxide solution (600 μmol) are added portionwiseto 112 mg of 21 (366 μmol) in methanol (4 mL). The solution is refluxedfor two hours. After evaporating off the solvent, the reaction medium isacidified with 0.5 N HCl and extracted with DCM. 107 mg of the expectedacid are obtained in the form of a white solid, i.e. a yield of 99%.

¹H NMR (250 MHz, CDCl₃) δ (ppm):

7.70 (d, 1H, ArH-6, J_(6.5) 7.8Hz), 7.62 (m, 1H, ArH-2), 7.38 (dd, 1H,ArH-5, J_(5.4) 8.0Hz), 7.16 (dd, 1H, ArH-4, J_(4.2) 2.1Hz), 4.02 (t, 2H,CH ₂—OAr, J 6.5Hz), 1.99 (tt, 2H, ArO—CH₂—CH ₂—CH₂, J 6.6Hz), 1.55−1.20(m, 16H, 8 CH ₂), 0.89 (t, 3H, CH ₃, J 6.5Hz)

¹³C NMR (62.5 MHz, CDCl₃) δ (ppm):

171 (CO₂H), 159 (C-3), 130 (C-1), 129 (C-5), 122 (C-6), 121 (C-4), 115(C-2), 68 (CH₂—OAr), 32-23 (9 CH₂), 14 (CH₃)

Mass spectrum:

Negative ESI m/z=291.2 [M-H]−

High res. Calc. for C₁₈H₂₇O₃: 291.196020, Found: 291.196560

Infrared (cm⁻¹):2950-2920-2850-2700-2400-1680-1603-1455-1420-1312-1247-757

Melting point: 88° C.

3-(undecanyloxy)benzoyl chloride (23)

1 mL of oxalyl chloride (11.5 mmol) and two drops of anhydrous DMF areadded under argon to 93 mg of toluene-dried acid 22 (318 μmol) dissolvedin 20 mL of anhydrous DCM. The medium is stirred at room temperature fortwo hours, and then concentrated to give 99 mg of a yellow oil, i.e. ayield of 99%.

methyl 3-(undec-4-ynyloxy)benzoate (25)

325 mg of 14 (2.14 mmol) and 300 mg of K₂CO₃ (2.17 mmol) are added to600 mg of 24 (2.16 mmol) in anhydrous DMF (7 mL). After reaction for 6hours at 90° C., the reaction medium is concentrated, washed with DCMand then taken up in water. 639 mg of a yellow oil are obtained, and arechromatographed on silica gel in pentane/ethyl acetate (50/1). 429 mg ofa yellow oil are isolated, i.e. a yield of 66%.

¹H NMR (200 MHz, CDCl₃) δ (ppm):

7.63 (m, 1H, ArH-6), 7.57 (m, 1H, ArH-2), 7.31 (dd, 1H, ArH-5, J_(5.4)8.1Hz and J_(5.6) 7.8Hz), 7.11 (ddd, 1H, ArH-4, J_(4.6) 2.4Hz andJ_(4.2) 0.8Hz), 4.11 (t, 2H, CH ₂—OAr, J 6.2Hz), 3.92 (s, 3H, OCH ₃),2.39−2.15 (2 m, 4H, CH ₂—C═C—CH ₂), 1.98 (tt, 2H, ArO—CH₂—CH ₂—CH₂—C≡C,J 6.5Hz), 1.52−1.23 (m, 8H, 4 CH ₂), 0.88 (t, 3H, CH ₃, J 6.7Hz)

¹³C NMR (62.5 MHz, CDCl₃) δ (ppm):

167 (CO₂ CH₃), 159 (C-3), 131 (C-1), 129 (C-5), 122 (C-6), 120 (C-4),115 (C-2), 81−79 (C≡C), 67 (CH₂—OAr), 52 (CH₃O), 31−15 (7 CH₂), 14 (CH₃)

Mass spectrum:

Positive ESI m/z=325.1 [M+Na]+

High res. Calc. for C₁₉H₂₆O₃Na: 325.177964, Found: 325.178070

Infrared (cm⁻¹): 2950-2931-2857-1726-1586-1446-1288-1228-756

3-(undec-4-ynyloxy)benzoic acid (26)

300 μL of 1 N sodium hydroxide solution (300 μmol) are added portionwiseto 48 mg of 25 (157 μmol) in methanol (2 mL). The solution is refluxedfor 1 hour 30 minutes. After evaporating off the solvent, the reactionmedium is acidified with 0.5 N HCl and extracted with DCM. 45 mg of apale yellow oil are obtained, i.e. a yield of 99%.

¹H NMR (250 MHz, CDCl₃) δ (ppm):

11.00−10.00 (bd, 1H, CO₂ H), 7.72 (d, 1H, ArH-6, J_(6.5) 7.7Hz), 7.64(m, 1H, ArH-2), 7.38 (dd, 1H, ArH-5, J_(5.4) 8.1Hz), 7.17 (dd, 1H,ArH-4, J_(4.2) 2.7Hz), 4.13 (t, 2H, CH ₂—OAr, J 6.1Hz), 2.39−2.15 (2 m,4H, CH ₂—C≡C—CH ₂), 1.99 (tt, 2H, ArO—CH₂—CH ₂—CH₂—C≡C, J 6.5Hz),1.50−1.20 (m, 8H, 4 CH ₂), 0.88 (t, 3H, CH ₃, J 6.7Hz)

¹³C NMR (62.5 MHz, CDCl₃) δ (ppm):

172 (CO₂H), 159 (C-3), 131 (C-1), 129 (C-5), 123 (C-6), 121 (C-4), 115(C-2), 81-79 (C≡C), 67 (CH₂—OAr), 31−15 (7 CH₂), 14 (CH₃)

Mass spectrum:

Negative ESI m/z=287.1 [M-H]−

High res. Calc. for C₁₈H₂₃O₃: 287.164719, Found: 287.164820

Infrared (cm⁻¹):2954-2929-2855-2700-2400-1690-1592-1452-1414-1288-1247-756

3-(undec-4Z-ynyloxy)benzoyl chloride (27)

850 μL of oxalyl chloride (9.74 mmol) and two drops of anhydrous DMF areadded under argon to 80 mg of toluene-dried acid 26 (278 μmol) dissolvedin 17 mL of anhydrous DCM. The medium is stirred at room temperature fortwo hours, and then concentrated to give 85 mg of a yellow oil, i.e. ayield of 99%.

methyl 2-(undec-4Z-enyloxy)benzoate (29)

88 mg of 28 (578 μmol) and 77 mg of K₂CO₃ (557 μmol) are added to 140 mgof 13 (500 μmol) in anhydrous DMF (2 mL). After reaction for 8 hours at90° C., the reaction medium is concentrated, taken up in DCM and thenwashed with water. 137 mg of a yellow oil are obtained, and arechromatographed on silica gel in pentane/ethyl acetate (40/1). 100 mg ofa yellow oil are isolated, i.e. a yield of 66%.

¹H NMR (250 MHz, CDCl₃) δ (ppm):

7.79 (dd, 1H, ArH-6, J_(6.5) 8.1Hz and J_(6.4) 1.9Hz), 7.43 (ddd, 1H,ArH-4, J_(4.3) 8.5Hz, J_(4.5) 7.3Hz), 6.94 (m, 2H, ArH-5 and ArH-3),5.40 (m, 2H, CH═CH), 4.02 (t, 2H, CH ₂—OAr, J 6.3Hz), 3.89 (s, 3H, OCH₃), 2.28−2.01 (2 m, 4H, CH ₂—CH═CH—CH ₂, J 6.6Hz), 1.89 (tt, 2H,ArO—CH₂—CH ₂—CH₂, J 6.6Hz), 1.50−1.16 (m, 8H, 4 CH ₂), 0.86 (t, 3H, CH₃, J 6.6Hz)

¹³C NMR (62.5 MHz, CDCl₃) δ (ppm):

167 (C═O), 158 (C-2), 133 (C-4), 131 (CH═CH), 128 (C-6), 120 (C-1), 119(C-5), 113 (C-3), 68 (CH₂—OAr), 52 (CH₃O), 32-22 (7 CH₂), 14 (CH₃)

Mass spectrum:

Positive ESI m/z=327.2 [M+Na]+

High res. Calc. for C₁₉H₂₈O₃Na: 327.193914, Found: 327.192560

Infrared (cm⁻¹): 3000-2962-2925-2855-1734-1601-1491-1456-1305-1250-754

2-(undec-4Z-enyloxy)benzoic acid (30)

500 μL of 1 N sodium hydroxide solution (500 μmol) are added portionwiseto 80 mg of 29 (263 μmol) in methanol (3 mL). The solution is refluxedfor 24 hours. After evaporating off the solvent, the reaction medium isacidified with 0.5 N HCl and extracted with DCM. 76 mg of a yellow oilare obtained, i.e. a yield of 99%.

¹H NMR (250 MHz, CDCl₃) δ (ppm):

12.00−10.00 (bd, 1H, CO₂ H), 8.16 (dd, 1H, ArH-6, J_(6.5) 7.8Hz andJ_(6.4) 1.9Hz), 7.54 (ddd, 1H, ArH-4, J_(4.3) 8.4Hz and J_(4.5) 7.6Hz),7.10 (ddd, 1H, ArH-5, J_(5.3) 0.8Hz), 7.03 (dd, 1H, ArH-3), 5.40 (m, 2H,CH═CH), 4.24 (t, 2H, CH ₂—OAr, J 6.4Hz), 2.25 (m, 2H, CH ₂—CH═CH—CH₂),1.97 (m, 4H, ArO—CH₂—CH ₂—CH₂—CH═CH—CH ₂), 1.35−1.10 (m, 8H, 4 CH ₂),0.84 (t, 3H, CH ₃, J 6.6Hz)

¹³C NMR (62.5 MHz, CDCl₃) δ (ppm):

165 (CO₂H), 157 (C-2), 135 (C-4), 134−132 (CH═CH), 127 (C-6), 122 (C-5),117 (C-1), 112 (C-3), 69 (CH₂—OAr), 32−22 (7 CH₂), 14 (CH₃)

Mass spectrum:

Negative ESI m/z=289.2 [M-H]−

High res. Calc. for C₁₈H₂₅O₃: 289.180370, Found: 289.179060

2-(undec-4Z-enyloxy)benzoyl chloride (31)

800 μL of oxalyl chloride (9.17 mmol) and two drops of anhydrous DMF areadded under argon to 76 mg of toluene-dried acid 30 (262 μmol) dissolvedin 15 mL of anhydrous DCM. The medium is stirred at room temperature fortwo hours and then concentrated to give 80 mg of a yellow oil, i.e. ayield of 99%.

¹H NMR (250 MHz, CDCl₃) δ (ppm):

7.97 (dd, 1H, ArH-6, J_(6.5) 7.9Hz and J_(6.4) 1.7Hz), 7.46 (m, 1H,ArH-4), 6.90 (m, 2H, ArH-5 and ArH-3), 5.30 (m, 2H, CH═CH), 3.95 (t, 2H,CH ₂—OAr, J 6.3Hz), 2.20−1.90 (2 m, 4H, CH ₂—CH═CH—CH ₂), 1.79 (tt, 2H,ArO—CH₂—CH ₂—CH₂—CH═CH, J 6.6Hz), 1.20−1.09 (m, 8H, 4 CH ₂), 0.76 (t,3H, CH ₃, J 6.7Hz)

methyl 4-(undec-4Z-enyloxy)benzoate (33)

90 mg of 32 (590 μmol) and 81 mg of K₂CO₃ (590 μmol) are added to 150 mgof 13 (535 μmol) in anhydrous DMF (2 mL). After reaction for 7 hours at90° C., the reaction medium is concentrated, taken up in DCM and thenwashed with water. 163 mg of a yellow oil are obtained, and arechromatographed on silica gel in pentane/ethyl acetate (80/1). 129 mg ofthe expected coupling product are isolated in the form of a yellow oil,i.e. a yield of 79%.

¹H NMR (250 MHz, CDCl₃) δ (ppm):

7.97 (d, 2H, ArH-2 and ArH-6, J_(6.5)=J_(2.3) 8.8Hz), 6.89 (d, 2H, ArH-3and ArH-5), 5.39 (m, 2H, CH═CH), 3.99 (t, 2H, CH ₂—OAr, J 6.3Hz), 3.88(s, 3H, OCH ₃), 2.22−2.00 (2 m, 4H, CH ₂—CH═CH—CH ₂), 1.84 (tt, 2H,ArO—CH₂—CH ₂—CH₂, J 6.8Hz), 1.40−1.12 (m, 8H, 4 CH ₂), 0.85 (t, 3H, CH₃, J 6.6Hz)

¹³C NMR (62.5 MHz, CDCl₃) δ (ppm):167 (C═O), 163 (C-4), 131 (C-2 andC-6), 130−128 (CH═CH), 122 (C-1), 114 (C-5 and C-3), 67 (CH₂—OAr), 52(CH₃O), 32−23 (7 CH₂), 14 (CH₃)

Mass spectrum:

Positive ESI m/z=327.2 [M+Na]+

High res. Calc. for C₁₉H₂₈O₃Na: 327.193914, Found: 327.192630

Infrared (cm⁻¹): 3000-2962-2925-2855-1720-1607-1511-1435-1279-1254-846

4-(undec-4Z-enyloxy)benzoic acid (34)

550 μL of 1 N sodium hydroxide solution (550 μmol) are added portionwiseto 109 mg of 33 (358 μmol) in methanol (4 mL). The solution is refluxedfor 20 hours. After evaporating off the solvent, the reaction medium isacidified with 0.5 N HCl and extracted with DCM. 102 mg of a white solidare obtained, i.e. a yield of 98%.

¹H NMR (250 MHz, CDCl₃) δ (ppm):

12.00−11.00 (bd, 1H, CO₂ H), 8.07 (d, 2H, ArH-2 and ArH-6,J_(2.3)=J_(6.5) 8.5Hz), 6.94 (d, 2H, ArH-3 and ArH-5), 5.42 (m, 2H,CH═CH), 4.03 (t, 2H, CH ₂—OAr, J 6.3Hz), 2.26−2.03 (2 m, 4H, CH₂—CH═CH—CH ₂), 1.88 (tt, 2H, ArO—CH₂—CH ₂—CH₂, J 6.8Hz), 1.40−1.10 (m,8H, 4 CH ₂), 0.89 (t, 3H, CH ₃, J 6.6Hz)

¹³C NMR (62.5 MHz, CDCl₃) δ (ppm):

172 (CO₂H), 164 (C-4), 132 (C-2 and C-6), 131-128 (CH═CH), 121 (C-1),114 (C-3 and C-5), 67 (CH₂—OAr), 32−22 (7 CH₂), 14 (CH₃)

Mass spectrum:

Negative ESI m/z=289.2 [M-H]−

High res. Calc. for C₁H₂₅O₃: 289.180370, Found: 289.178710

4-(undec-4Z-enyloxy)benzoyl chloride (35)

1 mL of oxalyl chloride (11.5 mmol) and two drops of anhydrous DMF areadded under argon to 101 mg of toluene-dried acid 34 (348 μmol)dissolved in 18 mL of anhydrous DCM. The medium is stirred at roomtemperature for two hours and then concentrated to give 107 mg of ayellow oil, i.e. a yield of 99%.

¹H NMR (250 MHz, CDCl₃) δ (ppm):

7.96 (d, 2H, ArH-2 and ArH-6, J_(2.3)=J_(6.5) 8.7Hz), 6.99 (d, 2H, ArH-3and ArH-5), 5.43 (m, 2H, CH═CH), 4.10 (t, 2H, CH ₂—OAr, J 6.3Hz),2.27−2.03 (2 m, 4H, CH ₂—CH═CH—CH ₂), 1.91 (tt, 2H, ArO—CH₂—CH₂—CH ₂, J6.7Hz), 1.35−1.12 (m, 8H, 4 CH ₂), 0.89 (t, 3H, CH ₃, J 6.6Hz)

1. A compound of formula (I)

in which n represents 1, 2 or 3; A represents a substituent selectedfrom the group consisting of —C(O)—, —C(S)—, and —CH₂—; B is selectedfrom the group consisting of an arylene and a naphthylene, these groupsoptionally being substituted with one or two substituents independentlyselected from the group consisting of halogen, CN, C(O)OR¹⁴,C(O)NR¹⁵R¹⁶, CF₃, OCF₃, —NO₂, N₃, OR¹⁴, SR¹⁴, NR¹⁵R¹⁶ and C₁₋₆-alkyl,wherein R¹⁴, R¹⁵, and R¹⁶ are independently selected from the groupconsisting of H, C₁₋₆-alkyl, C(O)C₁₋₆-alkyl, —C(S)C₁₋₆-alkyl,—C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂, —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl,—C(S)NHC₁₋₆-alkyl, and —C(NH)NHC₁₋₆-alkyl; C represents a substituentselected from the group consisting of —O—, —S—, —CH₂—, andCH—(C₁₋₆-alkyl); D represents a linear or branched, saturated orunsaturated hydrocarbon-based chain containing from 2 to 20 carbonatoms; E and G represent, independently of each other, a substituentselected from the group consisting of H, OH, OC(O)CH₃ and NHC(O)CH₃; R₁represents a substituent selected from the group consisting of H,C₁₋₆-alkyl C(O)H and C(O)CH₃; R², R³, and R⁶ represent, independently ofeach other, a substituent selected from the group consisting of H,C₁₋₆-alkyl, C(O)C₁₋₆-alkyl, —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂,—C(S)NH₂, —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and—C(NH)NHC₁₋₆-alkyl; R⁴ represents a substituent selected from the groupconsisting of H, C₁₋₆-alkyl and R²¹; R⁵ represents a substituentselected from the group consisting of H, C₁₋₆-alkyl, fucosyl and R²²; R⁷represents a substituent selected from the group consisting of H,C₁₋₆-alkyl, arabinosyl and R²³; R⁸ represents a substituent selectedfrom the group consisting of H, C₁₋₆-alkyl, fucosyl, methylfucosyl,sulfofucosyl, acetylfucosyl, arabinosyl, SO₃H, SO₃Li, SO₃Na, SO₃K,SO₃N(C₁₋₈alkyl)₄ and R²⁴; R⁹ represents a substituent selected from thegroup consisting of H, C₁₋₆-alkyl, mannose, glycerol and R²⁵; R²¹, R²²,R²³, R²⁴ and R²⁵ represent, independently of each other, a substituentselected from the group consisting of C(O)C₁₋₆-alkyl, —C(S)C₁₋₆-alkyl,—C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂, —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl,—C(S)NHC₁₋₆-alkyl and —C(NH)NHC₁₋₆-alkyl; and also the possiblegeometrical and/or optical isomers, enantiomers and/or diastereoisomers,tautomers, salts, N-oxides, sulfoxides, sulfones, and metal or metalloidcomplexes thereof that are agriculturally acceptable.
 2. The compound offormula (I) of claim 1, having at least one of the followingcharacteristics: n represents 2 or 3; A is selected from the groupconsisting of —C(O)— and —CH₂; B represents a phenylene; C represents—O—; D represents a linear, saturated or unsaturated hydrocarbon-basedchain containing from 3 to 17 carbon atoms; E and G represent NHC(O)CH₃;R¹ is selected from the group consisting of H, CH₃ and C(O)CH₃; R², R³,R⁵, R⁶, R⁷ and R⁹ represent H; R⁴ is selected from the group consistingof H, C(O)CH₃ or C(O)NH₂; R⁸ is selected from the group consisting of H,SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄, fucosyl and methylfucosyl.3. The compound of formula (I) of claim 1, wherein: n represents 2 or 3;A is selected from the group consisting of —C(O)— and —CH₂—; E and Grepresent NHC(O)CH₃; R¹ is selected from the group consisting of H, CH₃and C(O)CH₃; R², R³, R⁵, R⁶, R⁷ and R⁹ represent H; R⁴ is selected fromthe group consisting of H, C(O)CH₃ and C(O)NH₂; and R⁸ is selected fromthe group consisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,fucosyl and methylfucosyl.
 4. The compound of formula (I) of claim 1wherein: n represents 2 or 3; A is selected from the group consisting of—C(O)— and —CH₂—; D represents a linear, saturated or unsaturatedhydrocarbon-based chain containing from 3 to 17 carbon atoms; E and Grepresent NHC(O)CH₃; R¹ is selected from the group consisting of H, CH₃and C(O)CH₃; R², R³, R⁵, R⁶, R⁷ and R⁹ represent H; R⁴ is selected fromthe group consisting of H, C(O)CH₃ and C(O)NH₂; and R⁸ is selected fromthe group consisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,fucosyl and methylfucosyl.
 5. The compound of formula (I) of claim 1wherein: n represents 2 or 3; A is selected from the group consisting of—C(O)— and —CH₂—; C represents —O—; D represents a linear, saturated orunsaturated hydrocarbon-based chain containing from 3 to 17 carbonatoms; E and G represent NHC(O)CH₃; R¹ is selected from the groupconsisting of H, CH₃ and C(O)CH₃; R², R³, R⁵, R⁶, R⁷ and R⁹ represent H;R⁴ is selected from the group consisting of H, C(O)CH₃ and C(O)NH₂; andR⁸ is selected from the group consisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K,SO₃N(C₁₋₈alkyl)₄, fucosyl and methylfucosyl.
 6. The compound of formula(I) of claim 1 wherein: n represents 2 or 3; A is selected from thegroup consisting of —C(O)— and —CH₂—; B represents a phenylene; Crepresents —O—; D represents a linear hydrocarbon-based chain containing11 carbons, which is saturated, or unsaturated between carbons 4 and 5;E and G represent NHC(O)CH₃; R¹ is selected from the group consisting ofH, CH₃ or C(O)CH₃; R², R³, R⁵, R⁶, R⁷ and R⁹ represent H; R⁴ is selectedfrom the group consisting of H, C(O)CH₃ and C(O)NH₂; and ⁸ is selectedfrom the group consisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K,SO₃N(C₁₋₈alkyl)₄, fucosyl and methylfucosyl.
 7. The compound as claimedin claim 1 and of formula (Ia)

in which n represents 1, 2 or 3, B is selected from the group consistingof an arylene and a naphthylene; C represents a substituent selectedfrom the group consisting of —O—, —S—, —CH₂—, and CH—(C₁-C₆alkyl); Drepresents a linear or branched, saturated or unsaturatedhydrocarbon-based chain containing from 2 to 20 carbon atoms; E and Grepresent, independently of each other, a substituent selected from thegroup consisting of H, OH, OC(O)CH₃ and NHC(O)CH₃; R¹ represents asubstituent selected from the group consisting of H, C₁₋₆-alkyl, C(O)H,and C(O)CH₃; R², R³, and R⁶ represent, independently of each other, asubstituent selected from the group consisting of H, C₁₋₆-alkyl,C(O)C₁₋₆-alkyl, —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,—C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and —C(NH)NHC₁₋₆-alkyl;R⁴ represents a substituent selected from the group consisting of H,C₁₋₆-alkyl and R²¹; R⁵ represents a substituent selected from the groupconsisting of H, C₁₋₆-alkyl, fucosyl and R²²; R⁷ represents asubstituent selected from the group consisting of H, C₁₋₆-alkyl,arabinosyl and R²³; R⁸ represents a substituent selected from the groupconsisting of H, C₁₋₆-alkyl, fucosyl, methylfucosyl, sulfofucosyl,acetylfucosyl, arabinosyl, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄and R²⁴; R⁹ represents a substituent selected from the group consistingof H, C₁₋₆-alkyl, mannose, glycerol and R²⁵; R²¹, R²², R²³, R²⁴ and R²⁵represent, independently of each other, a substituent selected from thegroup consisting of C(O)C₁₋₆-alkyl, —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl,—C(O)NH₂, —C(S)NH₂, —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and—C(NH)NHC₁₋₆-alkyl; and also the possible geometrical and/or opticalisomers, enantiomers and/or diastereoisomers, tautomers, salts,N-oxides, sulfoxides, sulfones, and metal or metalloid complexesthereof.
 8. The compound of formula (Ia) of claim 7, having at least oneor other of the following characteristics: n represents 2 or 3; Brepresents a phenylene; C represents —O—; D represents a linear,saturated or unsaturated hydrocarbon-based chain containing from 3 to 17carbon atoms; E and G represent NHC(O)CH₃; R¹ is selected from the groupconsisting of H and CH₃; R², R³, R⁵, R⁶, R⁷ and R⁹ represent H; R⁴ isselected from the group consisting of H, C(O)CH₃ and C(O)NH₂; R⁸ isselected from the group consisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K,SO₃N(C₁₋₈alkyl)₄, fucosyl and methylfucosyl.
 9. The compound of formula(Ia) of claim 7 wherein: n represents 2 or 3; E and G representNHC(O)CH₃; R¹ is selected from the group consisting of H and CH₃; R²,R³, R⁵, R⁶, R⁷ and R⁹ represent H; R⁴ is selected from the groupconsisting of H, C(O)CH₃ and C(O)NH₂; R⁸ is selected from the groupconsisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄, fucosyl andmethylfucosyl.
 10. The compound of formula (Ia) of claim 7 wherein: nrepresents 2 or 3; D represents a linear, saturated or unsaturatedhydrocarbon-based chain containing from 3 to 17 carbon atoms; E and Grepresent NHC(O)CH₃; R¹ is selected from the group consisting of H andCH₃; R², R³, R⁵, R⁶, R⁷ and R⁹ represent H; R⁴ is selected from thegroup consisting of H, C(O)CH₃ and C(O)NH₂; R⁸ is selected from thegroup consisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,fucosyl and methylfucosyl.
 11. The compound of formula (Ia) of claim 7wherein: n represents 2 or 3; C represents —O—; D represents a linear,saturated or unsaturated hydrocarbon-based chain containing from 3 to 17carbon atoms; E and G represent NHC(O)CH₃; R¹ is selected from the groupconsisting of H and CH₃; R², R³, R⁵, R⁶, R⁷ and R⁹ represent H; R⁴ isselected from the group consisting of H, C(O)CH₃ and C(O)NH₂; R⁸ isselected from the group consisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K,SO₃N(C₁₋₈alkyl)₄, fucosyl and methylfucosyl.
 12. The compound of formula(Ia) of claim 7 wherein: n represents 2 or 3; B represents a phenylene;C represents —O—; D represents a linear hydrocarbon-based chaincontaining 11 carbons, which is saturated, or unsaturated betweencarbons 4 and 5; E and G represent NHC(O)CH₃; R¹ is selected from thegroup consisting of H and CH₃; R², R³, R⁵, R⁶, R⁷, and R⁹ represent H;R⁴ is selected from the group consisting of H, C(O)CH₃ and C(O)NH₂; R⁸is selected from the group consisting of H, SO₃H, SO₃Li, SO₃Na, SO₃KSO₃N(C₁₋₈alkyl)₄, fucosyl and methylfucosyl.
 13. The compound as claimedin claim 1 and of formula (Ib)

in which n represents 1, 2 or 3, B is selected from the group consistingof an arylene; and a naphthylene; C represents a substituent selectedfrom the group consisting of —O—, —S—, —CH₂—,and CH—(C₁₋₆-alkyl); Drepresents a linear or branched, saturated or unsaturatedhydrocarbon-based chain containing from 2 to 20 carbon atoms; E and Grepresent, independently of each other, a substituent selected from thegroup consisting of H, OH, OCO(CH₃) and NHC(O)CH₃; R¹ represents asubstituent selected from the group consisting of H, C₁₋₆-alkyl, C(O)H,and C(O)CH₃; R², R³, and R⁶ represent, independently of each other, asubstituent selected from the group consisting of H, C₁₋₆-alkyl,C(O)C₁₋₆-alkyl, —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂,—C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and —C(NH)NHC₁₋₆-alkyl;R⁴ represents a substituent selected from the group consisting of H,C₁₋₆-alkyl and R²¹; R⁵ represents a substituent selected from the groupconsisting of H, C₁₋₆-alkyl, fucosyl and R²²; R⁷ represents asubstituent selected from the group consisting of H, C₁₋₆-alkyl,arabinosyl and R²³; R⁸ represents a substituent selected from the groupconsisting of H, C₁₋₆-alkyl, fucosyl, methylfucosyl, sulfofucosyl,acetylfucosyl, arabinosyl, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄and R²⁴; R⁹ represents a substituent selected from the group consistingof H, C₁₋₆-alkyl, mannose, glycerol and R²⁵; R¹⁴, R¹⁵, R¹⁶ and R¹⁹represent, independently of each other, a substituent selected from thegroup consisting of H, C₁₋₆-alkyl, —C(O)C₁₋₆-alkyl, —C(S)C₁₋₆-alkyl,—C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂, —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl,—C(S)NHC₁₋₆-alkyl and —C(NH)NHC₁₋₆-alkyl; R²¹, R²², R²³, R²⁴ and R²⁵represent, independently of each other, a substituent selected from thegroup consisting of C(O)C₁₋₆-alkyl, —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl,—C(O)NH₂, —C(S)NH₂, —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and—C(NH)NHC₁₋₆-alkyl; and also the possible geometrical and/or opticalisomers, enantiomers and/or diastereoisomers, tautomers, salts,N-oxides, sulfoxides, sulfones, and metal or metalloid complexes thereofthat are agriculturally acceptable.
 14. The compound of formula (Ib) ofclaim 13, having at least one of the following characteristics: nrepresents 2 or 3; B represents a phenylene; C represents —O—; Drepresents a linear, saturated or unsaturated hydrocarbon-based chaincontaining from 3 to 17 carbon atoms; E and G represent NHC(O)CH₃; R¹ isselected from the group consisting of H and C(O)CH₃; R², R³, R⁵, R⁶, R⁷and R⁹ represent H; R⁴ is selected from the group consisting of H,C(O)CH₃ and C(O)NH₂; R⁸ is selected from the group consisting of H,SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄, fucosyl and methylfucosyl.15. The compound of formula (Ib) of claim 13 wherein: n represents 2 or3; E and G represent NHC(O)CH₃; R¹ is selected from the group consistingof H and C(O)CH₃; R², R³, R⁵, R⁶, R⁷ and R⁹ represent H; R⁴ is selectedfrom the group consisting of H, C(O)CH₃ and C(O)NH₂; R⁸ is selected fromthe group consisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,fucosyl and methylfucosyl.
 16. The compound of formula (Ib) of claim 13wherein: n represents 2 or 3; D represents a linear, saturated orunsaturated hydrocarbon-based chain containing from 3 to 17 carbonatoms; E and G represent NHC(O)CH₃; R¹ is selected from the groupconsisting of H and C(O)CH₃; R², R³, R⁵, R⁶, R⁷ and R⁹ represent H; R⁴is selected from the group consisting of H, C(O)CH₃ and C(O)NH₂; R⁸ isselected from the group consisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K,SO₃N(C₁₋₈alkyl)₄, fucosyl and methylfucosyl.
 17. The compound of formula(Ib) of claim 13 wherein: n represents 2 or 3; C represents —O—; Drepresents a linear, saturated or unsaturated hydrocarbon-based chaincontaining from 3 to 17 carbon atoms; E and G represent NHC(O)CH₃; R¹ isselected from the group consisting of H and C(O)CH₃; R², R³, R⁵, R⁶, R⁷and R⁹ represent H; R⁴ is selected from the group consisting of H,C(O)CH₃ and C(O)NH₂; R⁸ is selected from the group consisting of H,SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄, fucosyl and methylfucosyl.18. The compound of formula (Ib) of claim 13 wherein: n represents 2 or3; B represents a phenylene; C represents —O—; D represents a linearhydrocarbon-based chain containing 11 carbons, which is saturated, orunsaturated between carbons 4 and 5; E and G represent NHC(O)CH₃; R¹ isselected from the group consisting of H and C(O)CH₃; R², R³, R⁵, R⁶, R⁷and R⁹ represent H; R⁴ is selected from the group consisting of H,C(O)CH₃ and C(O)NH₂; R⁸ is selected from the group consisting of H,SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄, fucosyl and methylfucosyl.19. The compound as claimed in claim 1 and of formula (Ic)

in which n represents 1, 2 or 3; A represents a substituent selectedfrom the group consisting of —C(O)—, —C(S)—, and —CH₂—; B is selectedfrom the group consisting of an arylene and a naphthylene; D representsa linear or branched, saturated or unsaturated hydrocarbon-based chaincontaining from 2 to 20 carbon atoms; E and G represent, independentlyof each other, a substituent selected from the group consisting of H,OH, OC(O)CH₃ and NHC(O)CH₃; R¹ represents a substituent chosen from H, C₁₋₆-alkyl, C(O)H, and C(O)CH₃; R², R³, and R⁶ represent, independentlyof each other, a substituent selected from the group consisting of H,C₁₋₆-alkyl, C(O)C₁₋₆-alkyl, —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂,—C(S)NH₂, —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and—C(NH)NHC₁₋₆-alkyl; R⁴ represents a substituent selected from the groupconsisting of H, C₁₋₆-alkyl and R²¹; R⁵ represents a substituentselected from the group consisting of H, C₁₋₆-alkyl, fucosyl and R²²; R⁷represents a substituent selected from the group consisting of H,C₁₋₆-alkyl, arabinosyl and R²³ R⁸ represents a substituent selected fromthe group consisting of H, C₁₋₆-alkyl, fucosyl, methylfucosyl,sulfofucosyl, acetylfucosyl, arabinosyl, SO₃H, SO₃Li, SO₃Na, SO₃K,SO₃N(C₁₋₈alkyl)₄ and R²⁴; R⁹ represents a substituent selected from thegroup consisting of H, C₁₋₆-alkyl, mannose, glycerol and R²⁵; R²¹, R²²,R²³, R²⁴ and R²⁵ represent, independently of each other, a substituentselected from the group consisting of C(O)C₁₋₆-alkyl, —C(S)C₁₋₆-alkyl,—C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂, —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl,—C(S)NHC₁₋₆-alkyl and —C(NH)NHC₁₋₆-alkyl; and also the possiblegeometrical and/or optical isomers, enantiomers and/or diastereoisomers,tautomers, salts, N-oxides, sulfoxides, sulfones, and metal or metalloidcomplexes thereof that are agriculturally acceptable.
 20. The compoundof formula (Ic) of claim 19, having at least one of the followingcharacteristics: n represents 2 or 3; A is selected from the groupconsisting of —C(O)— and —CH₂—; B represents a phenylene; D represents alinear, saturated or unsaturated hydrocarbon-based chain containing from3 to 17 carbon atoms; E and G represent NHC(O)CH₃; R¹ is selected fromthe group consisting of H, CH₃ and C(O)CH₃; R², R³, R⁵, R⁶, R⁷ and R⁹represent H; R⁴ is selected from the group consisting of H, C(O)CH₃ andC(O)NH₂; R⁸ is selected from the group consisting of H, SO₃H, SO₃Li,SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄, fucosyl and methylfucosyl.
 21. Thecompound of formula (Ic) of claim 19 wherein: n represents 2 or 3; A isselected from the group consisting of —C(O)— and —CH₂—; E and Grepresent NHC(O)CH₃; R¹ is selected from the group consisting of H, CH₃and C(O)CH₃; R², R³, R⁵, R⁶, R⁷ and R⁹ represent H; R⁴ is selected fromthe group consisting of H, C(O)CH₃ and C(O)NH₂; R⁸ is selected from thegroup consisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,fucosyl and methylfucosyl.
 22. The compound of formula (Ic) of claim 19wherein: n represents 2 or 3; A is selected from the group consisting of—C(O)— and —CH₂—; D represents a linear, saturated or unsaturatedhydrocarbon-based chain containing from 3 to 17 carbon atoms; E and Grepresent NHC(O)CH₃; R^(l) is selected from the group consisting of H,CH₃ and C(O)CH₃; R², R³, R⁵, R⁶, R⁷ and R⁹ represent H; R⁴ is selectedfrom the group consisting of H, C(O)CH₃ and C(O)NH₂; R⁸ is selected fromthe group consisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,fucosyl and methylfucosyl.
 23. The compound of formula (Ic) of claim 19wherein: n represents 2 or 3; A is selected from the group consisting of—C(O)— and —CH₂—; B represents a phenylene; D represents a linearhydrocarbon-based chain containing 11 carbons, which is saturated, orunsaturated between carbons 4 and 5; E and G represent NHC(O)CH₃; R¹ isselected from the group consisting of H, CH₃ and C(O)CH₃; R¹ is selectedfrom the group consisting of H and CH₃; R², R³, R⁵, R⁶, R⁷ and R⁹represent H; R⁴ is selected from the group consisting of H, C(O)CH₃ andC(O)NH₂; R⁸ is selected from the group consisting of H, SO₃H, SO₃Li,SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄, fucosyl and methylfucosyl.
 24. Thecompound as claimed in claim 1 and of formula (Id)

in which n represents 1, 2 or 3; B is selected from the group consistingof an arylene and a naphthylene; D represents a linear or branched,saturated or unsaturated hydrocarbon-based chain containing from 2 to 20carbon atoms; E and G represent, independently of each other, asubstituent selected from the group consisting of H, OH, OC(O)CH₃ andNHC(O)CH₃; R¹ represents a substituent selected from the groupconsisting of H, C₁₋₆-alkyl, C(O)H, and C(O)CH₃; R², R³, and R⁶represent, independently of each other, a substituent selected from thegroup consisting of H, C₁₋₆-alkyl, C(O)C₁₋₆-alkyl, —C(S)C₁₋₆-alkyl,—C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂, —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl,—C(S)NHC₁₋₆-alkyl and —C(NH)NHC₁₋₆-alkyl; R⁴ represents a substituentselected from the group consisting of H, C₁₋₆-alkyl and R²¹; R⁵represents a substituent selected from the group consisting of H,C₁₋₆-alkyl, fucosyl and R²²; R⁷ represents a substituent selected fromthe group consisting of H, C₁₋₆-alkyl, arabinosyl and R²³; R⁸ representsa substituent selected from the group consisting of H, C₁₋₆-alkyl,fucosyl, methylfucosyl, sulfofucosyl, acetylfucosyl, arabinosyl, SO₃H,SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄ and R²⁴; R⁹ represents asubstituent selected from the group consisting of H, C₁₋₆-alkyl,mannose, glycerol and R²⁵; R²¹, R²², R²³, R²⁴ and R²⁵ represent,independently of each other, a substituent selected from the groupconsisting of C(O)C₁₋₆-alkyl, —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl,—C(O)NH₂, —C(S)NH₂, —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and—C(NH)NHC₁₋₆-alkyl; and also the possible geometrical and/or opticalisomers, enantiomers and/or diastereoisomers, tautomers, salts,N-oxides, sulfoxides, sulfones, and metal or metalloid complexesthereof, that are agriculturally acceptable.
 25. The compound of formula(Id) of claim 24, having at least one of the following characteristics:n represents 2 or 3; B represents a phenylene; D represents a linear,saturated or unsaturated hydrocarbon-based chain containing from 3 to 17carbon atoms; E and G represent NHC(O)CH₃; R¹ is selected from the groupconsisting of H and CH₃; R², R³, R⁵, R⁶, R⁷ and R⁹ represent H; R⁴ isselected from the group consisting of H, C(O)CH₃ and C(O)NH₉; R⁸ isselected from the group consisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K,SO₃N(C₁₋₈alkyl)₄, fucosyl and methylfucosyl.
 26. The compound of formula(Id) of claim 24 wherein: n represents 2 or 3; E and G representNHC(O)CH₃; R¹ is selected from the group consisting of H and CH₃; R²,R³, R⁵, R⁶, R⁷ and R⁹ represent H; R⁴ is selected from the groupconsisting of H, C(O)CH₃ and C(O)NH₂; R⁸ is selected from the groupconsisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄, fucosyl andmethylfucosyl.
 27. The compound of formula (Id) of claim 24 wherein: nrepresents 2 or 3; D represents a linear, saturated or unsaturatedhydrocarbon-based chain containing from 3 to 17 carbon atoms; E and Grepresent NHC(O)CH₃; R¹ is selected from the group consisting of H andCH₃; R², R³, R⁵, R^(6, R) ⁷ and R⁹ represent H; R⁴ is selected from thegroup consisting of H, C(O)CH₃ and C(O)NH₂; R⁸ is selected from thegroup consisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄,fucosyl and methylfucosyl.
 28. The compound of formula (Id) of claim 24wherein: n represents 2 or 3; B represents a phenylene; D represents alinear hydrocarbon-based chain containing 11 carbons, which issaturated, or unsaturated between carbons 4 and 5; E and G representNHC(O)CH₃; R¹ is selected from the group consisting of H and CH₃; R²,R³, R⁵, R⁶, R⁷ and R⁹ represent H; R⁴ is selected from the groupconsisting of H, C(O)CH₃ and C(O)NH₂; R⁸ is selected from, the groupconsisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄ fucosyl andmethylfucosyl.
 29. The compound of claim 1 and of formula (Ie)

in which n represents 1, 2 or 3; B is selected from the group consistingof an arylene; and a naphthylene; D represents a linear or branched,saturated or unsaturated hydrocarbon-based chain containing from 2 to 20carbon atoms; E and G represent, independently of each other, asubstituent selected from the group consisting of H, OH, OC(O)CH₃ andNHC(O)CH₃; R¹ represents a substituent selected from the groupconsisting of H, C₁₋₆-alkyl, C(O)H, and C(O)CH₃; R², R³, and R⁶represent, independently of each other, a substituent selected from thegroup consisting of H, C₁₋₆-alkyl, C(O)C₁₋₆-alkyl, —C(S)C₁₋₆-alkyl,—C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂, —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl,—C(S)NHC₁₋₆-alkyl and —C(NH)NHC₁₋₆-alkyl; R⁴ represents a substituentselected from the group consisting of H, C₁₋₆-alkyl and R²¹; R⁵represents a substituent selected from the group consisting of H,C₁₋₆-alkyl, fucosyl and R²²; R⁷ represents a substituent selected fromthe group consisting of H, C₁₋₆-alkyl, arabinosyl and R²³; R⁸ representsa substituent selected from the group consisting of H, C₁₋₆-alkyl,fucosyl, methylfucosyl, sulfofucosyl, acetylfucosyl, arabinosyl, SO₃H,SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄ and R²⁴; R⁹ represents asubstituent selected from the group consisting of H, C₁₋₆-alkyl,mannose, glycerol and R²⁵; R¹⁴, R¹⁵, R¹⁶ and R¹⁹ represent,independently of each other, a substituent selected from the groupconsisting of H, C₁₋₆-alkyl, —C(O)C₁₋₆-alkyl, —C(S)C₁₋₆-alkyl,—C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂, —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl,—C(S)NHC₁₋₆-alkyl and —C(NH)NHC₁₋₆-alkyl; R²¹, R²², R²³, R²⁴ and R²⁵represent, independently of each other, a substituent selected from thegroup consisting of C(O)C₁₋₆-alkyl, —C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl,—C(O)NH₂, —C(S)NH₂, —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and—C(NH)NHC₁₋₆-alkyl; and also the possible geometrical and/or opticalisomers, enantiomers and/or diastereoisomers, tautomers, salts,N-oxides, sulfoxides, sulfones, and metal or metalloid complexes thereofthat are agriculturally acceptable.
 30. The compound of formula (Ie) ofclaim 29, having at least one of the following characteristics: nrepresents 2 or 3; B represents a phenylene; D represents a linear,saturated or unsaturated hydrocarbon-based chain containing from 3 to 17carbon atoms; E and G represent NHC(O)CH₃; R¹ is selected the groupconsisting of H and C(O)CH₃; R², R³, R⁵, R⁶, R⁷ and R⁹ represent H; R⁴is selected the group consisting of H, C(O)CH₃ and C(O)NH₂; R⁸ isselected the group consisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K,SO₃N(C₁₋₈alkyl)₄, fucosyl or methylfucosyl.
 31. The compound of formula(Ie) of claim 29 wherein: n represents 2 or 3; E and G representNHC(O)CH₃; R¹ is selected the group consisting of H and C(O)CH₃; R², R³,R⁵, R⁶, R⁷ and R⁹ represent H; R⁴ is selected the group consisting of H,C(O)CH₃ and C(O)NH₂; R⁸ is selected the group consisting of H, SO₃H,SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄, fucosyl and methylfucosyl.
 32. Thecompound of formula (Ie) of claim 29 wherein: n represents 2 or 3; Drepresents a linear, saturated or unsaturated hydrocarbon-based chaincontaining from 3 to 17 carbon atoms; E and G represent NHC(O)CH₃; R¹ isselected the group consisting of H and C(O)CH₃; R², R³, R⁵, R⁶, R⁷ andR⁹ represent H; R⁴ is selected the group consisting of H, C(O)CH₃ andC(O)NH₂; R⁸ is selected the group consisting of H, SO₃H, SO₃Li, SO₃Na,SO₃K, SO₃N(C₁₋₈alkyl)₄, fucosyl or methylfucosyl.
 33. The compound offormula (Ie) of claim 29 wherein: n represents 2 or 3; B represents aphenylene; D represents a linear hydrocarbon-based chain containing 11carbons, which is saturated, or unsaturated between carbons 4 and 5; Eand G represent NHC(O)CH₃; R¹ is selected the group consisting of H andC(O)CH₃; R², R³, R⁵, R⁶, R⁷ and R⁹ represent H; R⁴ is selected the groupconsisting of H, C(O)CH₃ and C(O)NH₂; R⁸ is selected the groupconsisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄, fucosyl andmethylfucosyl.
 34. The compound of claim 1 wherein B represents anarylene optionally substituted with one or two substituentsindependently selected from the group consisting of halogen, CN,C(O)OR¹⁴, C(O)NR¹⁵R¹⁶, CF₃, OCF₃, —NO₂, N₃, OR¹⁴, SR¹⁴, NR¹⁵R¹⁶ andC₁₋₆-alkyl, wherein R¹⁴, R¹⁵, and R¹⁶ are independently selected fromthe group consisting of H, C₁₋₆-alkyl, C(O)C₁₋₆-alkyl, —C(S)C₁₋₆-alkyl,—C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂, —C(NH)NH₂, —C(O)NHC₁₋₆-alkyl,—C(S)NHC1-6-alkyl and —C(NH)NHC₁₋₆-alkyl.
 35. The compound of claim 1wherein B represents a phenylene optionally substituted with one or twosubstituents independently selected from the group consisting ofhalogen, CN, C(O)OR¹⁴, C(O)NR¹⁵R¹⁶, CF₃, OCF₃, —NO₂, N₃, OR¹⁴, SR¹⁴,NR¹⁵R¹⁶ and C₁₋₆-alkyl, wherein R¹⁴, R¹⁵, and R¹⁶ are independentlyselected from the group consisting of H, C₁₋₆-alkyl, C(O)C₁₋₆-alkyl,—C(S)C₁₋₆-alkyl, —C(O)OC₁₋₆-alkyl, —C(O)NH₂, —C(S)NH₂, —C(NH)NH₂,—C(O)NHC₁₋₆-alkyl, —C(S)NHC₁₋₆-alkyl and —C(NH)NHC₁₋₆-alkyl.
 36. Thecompound as claimed in claim 1, having at least one of the followingcharacteristics: n =2 or 3; A is selected from the group consisting of—C(O)—and —CH₂—; C represents —O—; E and G represent NHC(O)CH₃; R¹ isselected from the group consisting of H and C(O)CH₃; R², R³, R⁵, R⁶, andR⁷ represent a hydrogen atom; R⁴ represents a substituent selected fromthe group consisting of H, C(O)CH₃ and C(O)NH₂; R⁸ represents asubstituent selected from the group consisting of H, fucosyl,methylfucosyl, sulfofucosyl, acetylfucosyl, arabinosyl, SO₃H, SO₃Li,SO₃Na, SO₃K and SO₃N(C ₁₋₈alkyl)₄; R⁹ represents a hydrogen atom. 37.The compound of claim 1 wherein: n =2 or 3; A is selected from the groupconsisting of —C(O)—and —CH₂—; C represents —O—; E and G representNHC(O)CH₃; R¹ is selected from the group consisting of H or C(O)CH₃; R²,R³, R⁵, R⁶, and R⁷ represent a hydrogen atom; R⁴ represents asubstituent selected from the group consisting of H, C(O)CH₃ andC(O)NH₂; R⁸ represents a substituent selected from the group consistingof H, fucosyl, methylfucosyl, sulfofucosyl, acetylfucosyl, arabinosyl,SO₃H, SO₃Li, SO₃Na, SO₃K and SO₃N(C₁₋₈alkyl)₄; and R⁹ represents ahydrogen atom.
 38. The compound of claim 1 wherein R⁸ is selected fromthe group consisting of H, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃N(C₁₋₈alkyl)₄and a substituent of formula:

wherein R²⁶ represents a substituent selected from the group consistingof H and CH₃; R²⁷ and R²⁸ represent, independently of each other, asubstituent selected from the group consisting of H, C(O)CH₃, SO₃H,SO₃Li, SO₃Na, SO₃ and SO₃N(C₁₋₈alkyl)₄.
 39. The compound of claim 38wherein R²⁶, R²⁷ and R²⁸ each represents a hydrogen atom.
 40. Thecompound as claimed in claim 1, for which D represents a linear,saturated or unsaturated hydrocarbon-based chain containing from 7 to 15carbon atoms.
 41. The compound as claimed in claim 1, for which Drepresents a hydrocarbon-based chain according to one of the formulaerepresented below D1

D2

D3

D4

D5

D6

in which m=1 to 12 p=0 to 11 q=6 to 14 s=5 to 13 with m+p≦12 and m+p≧4.42. The compound of claim 1 wherein D represents a hydrocarbon-basedchain according to one of the formulae represented below D1

D2

D3

in which m=1 to 12 p=0 to 11 q=6 to 14 with m+p≦12 and m+≧4.
 43. Thecompound of claim 1 wherein D represents a linear hydrocarbon-basedchain comprising 11 carbon atoms, that is saturated, or unsaturatedbetween carbon atoms 4 and
 5. 44. The compound of claim 1, correspondingto one of the following formulae:

in which, when it is present, M represents a cation selected from theconsisting of H⁺, Li⁺, Na⁺, K⁺and (C₁₋₈alkyl)₄N⁺.
 45. The compound ofclaim 1 used as a nodulation factor for a plant.
 46. The nodulationfactor of claim 45 wherein said plant is a legume.
 47. The nodulationfactor of claim 46 wherein said legume is soybean, pea, horse bean,groundnut, bean, lupin, alfalfa or clover.
 48. The compound of claim 1used as a plant growth stimulation factor.
 49. The compound of claim 1wherein B is selected from the group consisting of:

wherein R¹² and R¹³ represent two substituents independently selectedfrom the group consisting of halogen, CN, CF₃, OCF₃, —NO₂, N₃, OR¹⁴,SR¹⁴, NR¹⁵R¹⁶ and C₁₋₆-alkyl.
 50. The compound of claim 49 wherein B is